# Patent

## Title
Cyclic amine compounds and agents for pest control

## Abstract

Agents for pest control comprising cyclic amine compounds represented by the formula (1)




or salts thereof or N-oxides thereof as an active ingredient,

    
    
        wherein Cy1 represents an unsubstituted or substituted 5-membered heterocycle or unsubstituted or substituted group represented by the formula (a) below,
    
    






    
    
        wherein Y1 and Y2 each independently represents nitrogen or carbon and symbol * represents the bonding positions.

## Background
FIELD OF THE INVENTION
The present invention relates to novel cyclic amine compounds and agents for pest control which contain these cyclic amine compounds or the like as active ingredients.
Priority is claimed on Japanese Patent Application No. 2005-294126, filed Oct. 6, 2005, Japanese Patent Application No. 2005-294127, filed Oct. 6, 2005, Japanese Patent Application No. 2005-297803, filed Oct. 12, 2005, Japanese Patent Application No. 2005-297804, filed Oct. 12, 2005, Japanese Patent Application No. 2006-016877, filed Jan. 25, 2006, and Japanese Patent Application No. 2006-182314, filed Jun. 30, 2006, the contents of which are incorporated herein by reference.
DESCRIPTION OF THE RELATED ART
Although many compounds which have insecticidal/acaricidal activities are conventionally known, there were problems such as insufficient effect thereof, limitation of use thereof because of drug resistance problems, occurrence of phytotoxicity or contamination in plant bodies, or strong toxicity against mammalians, fish, or the like.
The compounds represented by the formula below are known to have insecticidal/acaricidal activities.




In the formula, X represents O, S, NH, NR, or NOR; Y represents a bond (crosslink) or the like; Z represents C3 to C8-cycloalkyl or the like; and CH2 in these hydrocarbon rings in this case may be substituted with NR5 (R5 is phenyl or substituted phenyl). Known specific examples of such compounds include the compound represented by the formula below (refer to Patent document 1).





However, the structures of such compounds are limited to 4-aminopyridine derivatives and 4-hydroxypyridine derivatives and no compounds with other structures are specifically disclosed.

    [Patent document 1] Published Japanese translation No. Hei 09-502446 of PCT International Publication


DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
An object of the present invention is to provide agents for pest control, which can be synthesized industrially favorably, which have excellent bioactivities, which are problem-free in terms of safety, and which have the compounds with novel backbones as active ingredients.
Means for Solving the Problem
As a result of intensive research in order to solve the above problems, the present inventors discovered that novel cyclic amine compounds with a specific structure have excellent insecticidal/acaricidal activities to complete the present invention. In other words, the present invention firstly provides agents for pest control which are characterized by containing cyclic amine compounds represented by the formula (1), salts thereof, or N-oxides thereof, as active ingredients.




In the formula, Cy1 represents an unsubstituted or substituted 5-membered heterocycle or unsubstituted or substituted group represented by the formula (a) below.





[In the formula, Y1 and Y2 each independently represents nitrogen or carbon and the symbol (*) represents the bonding positions.]

X represents oxygen, sulfur, sulfinyl, sulfonyl, unsubstituted or substituted nitrogen.
Each R may bond to form a ring and R which does not bond to form a ring represents a hydroxyl, halogen, unsubstituted or substituted amino, nitro, or an organic group.
n is an integer from 0 to 9 and each R may be the same or different when n is 2 or more.
Cy2 represents unsubstituted or substituted cyclic hydrocarbon or unsubstituted or substituted heterocycle with a proviso that Cy2 is pyridin-2-yl, which is substituted with at least one or more cyano, when Cy1 is an unsubstituted or substituted phenyl and Cy2 is pyridin-2-yl.
The present invention secondly provides cyclic amine compounds represented by the formula (2), salts thereof, or N-oxides thereof.




In the formula, Cy3 represents any one of the formulae (b) to (h) below.





In the formula, R6 represents haloalkyl or haloalkoxy.
R7 represents unsubstituted or substituted alkoxy, unsubstituted or substituted alkoxycarbonyl, unsubstituted or substituted alkoxyalkyl, or the functional group represented by the formula (1) below.




[In the formula, R15 and R16 each independently represents hydrogen, unsubstituted or substituted hydrocarbon, unsubstituted or substituted heterocyclic group, unsubstituted or substituted amino, hydrocarbonoxy, or hydrocarbonthio. R15 and R16 may bond to form a ring, in that case, both two groups in the pair represent functional groups, which may integrate to form a ring, and Z1 represents oxygen or unsubstituted or substituted nitrogen.]

R8 to R14 each independently represents hydroxyl, thiol, halogen, nitro, formyl, cyano, haloalkyl, haloalkoxy, haloalkenyl, alkyl, (optionally substituted with G1), alkoxy (optionally substituted with G1), alkylcarbonyl, alkoxycarbonyl, alkyl, alkenyloxy, alknyloxy, aryl (optionally substituted with G1), or the functional group represented by the formula (1).
G1 represents hydroxyl, halogen, unsubstituted or substituted amino, nitro, or an organic group.
k, l, n and o each independently represents any one of an integer from 0 to 4 and each R8, R9, R10, R11, and R12 may be the same or different when k, l, n, and o are 2 or more.
m is any one of an integer from 0 to 5 and each R10 may be the same or different when m is 2 or more.
p and q each independently represents any one of an integer from 0 to 3 and each R13 and each R14 may be the same or different when p and q are 2 or more.
X represents oxygen, sulfur, sulfinyl, sulfonyl, or unsubstituted or substituted nitrogen.
R1a and R2a, R1a and R4a, R2a and R3a, or R3a and R4a may form saturated rings together and R1a, R1b, R1a, R2b, R3a, R3b, R4a, R4b, and R5 which do not form saturated rings together each independently represents a hydrogen, hydroxyl, halogen, unsubstituted or substituted amino, nitro, or an organic group.
Cy4 represents
pyridin-2-yl substituted with one or more cyano, pyridin-3-yl, pyridazin-3-yl, pyrazinyl, thiazol-2-yl, pyrimidin-2-yl, 1,3,4-thiadiazol-2-yl, or phenyl which are optionally substituted with G2 when Cy3 is a functional group represented by the formulae (c), (g), or (h),
pyridin-2-yl substituted with one or more cyano, pyridin-3-yl, pyridazin-3-yl, pyrazinyl, thiazol-2-yl, pyrimidin-2-yl, or 1,3,4-thiadiazol-2-yl which are optionally substituted with G2 when Cy3 is a functional group represented by the formulae (b), (e), or (f), and
pyridin-2-yl substituted with one or more cyano, pyrazinyl, or 1,3,4-thiadiazol-2-yl which are optionally substituted with G2 when Cy3 is a functional group represented by the formula (d).
G2 represents hydroxyl, halogen, cyano, nitro, formyl, alkyl (optionally substituted with G3), alkoxy (optionally substituted with G3), haloalkyl, haloalkoxy, alkylthiocarbonyl, alkylsulfonylamino, haloalkylsulfonylamino, bis(alkylsulfonyl)amino, bis(haloalkylsulfonyl)amino, alkoxycarbonyl, aryl (optionally substituted with G1), a 5 to 6-membered heterocyclic group (which contain at least one heteroatom out of oxygen, nitrogen, and sulfur), the group represented by the formulae (j) to (l).




In the formulae (j), (k), and (l), R17 and R18 each independently represents hydrogen, unsubstituted or substituted hydrocarbon, unsubstituted or substituted heterocyclic group, unsubstituted or substituted amino, hydrocarbonoxy, or hydrocarbonthio. R19 and R22 each independently represents hydrogen, unsubstituted or substituted hydrocarbon, unsubstituted or substituted heterocyclic group, or unsubstituted or substituted amino. R20 represents hydrogen or unsubstituted or substituted hydrocarbon. R21 represents hydrogen, unsubstituted or substituted hydrocarbon, or unsubstituted or substituted heterocyclic group. Y and Z each independently represents oxygen or unsubstituted or substituted nitrogen. R17 and R18, R19 and R20, and R21 and R22 may bond to form rings and in that case, both two groups in the pair represent functional groups, which may integrate to form a ring.

G3 represents hydroxyl, cyano, alkoxy, alkoxyalkoxy, or trialkylsilyloxy.
Effects of the Invention
According to the present invention, it is possible to provide agents for pest control with excellent bioactivities especially in terms of insecticidal/acaricidal activities and high safety and furthermore, it is possible to provide cyclic amine compounds with a novel structure, salts thereof, or N-oxides thereof.


PREFERRED EMBODIMENTS OF THE INVENTION
The present invention will be described in detail below.
I. Agents for Pest Control Containing Cyclic Amine Compounds Represented by the Formula (1), Salts Thereof, or N-oxides Thereof as Active Ingredients
The agents for pest control of the present invention are characterized by containing cyclic amine compounds represented by the formula (1), salts thereof, or N-oxides thereof, as active ingredients. In the formula (1), Cy1 is an unsubstituted or substituted 5-membered heterocyclic group or an unsubstituted or substituted functional group represented by the formula (a).
The 5-membered heterocyclic group is not particularly limited as long as it is a 5-membered heterocycle having one or more heteroatoms in the ring and it may be saturated or unsaturated. Specific examples thereof include pyrrolidin-2-yl, pyrrolidin-3-yl, furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, and 1,2,4-triazol-5-yl and thiophen-3-yl is preferable.
The formula (a) represents phenyl, pyridin-2-yl, pyridin-3-yl, or pyridazin-3-yl which are unsubstituted or substituted and unsubstituted or substituted phenyl is preferable.
Specific examples of the substituents of Cy1 include hydroxyl; thiol; halogen such as fluorine, chlorine, bromine, and iodine; cyano; nitro; formyl; unsubstituted or substituted amino such as amino, methylamino, benzylamino, anilino, dimethylamino, diethylamino, and phenylethylamino; alkyl (preferably C1-6 alkyl) such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sbutyl, isobutyl, t-butyl, n-pentyl, and n-hexyl; alkenyl such as vinyl, allyl, and 2-methoxyethenyl; alkynyl such as ethynyl, 1-propynyl, 2-phenylethynyl, and propargyl; alkoxy (preferably C1-6 alkoxy) such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, and t-butoxy; alkenyloxy such as vinyloxy and allyloxy; alkynyloxy such as ethynyloxy and propargyloxy; aryloxy such as phenoxy and benzyloxy; heteroaryloxy such as 2-pyridyloxy; haloalkyl (preferably C1-6 haloalkyl) such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, bromodifluoromethyl, 1,1,1-trifluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, and 2-bromoethyl, pentafluoroethyl; haloalkoxy (preferably C1-6 haloalkoxy) such as fluoromethoxy, chloromethoxy, bromomethoxy, difluoromethoxy, dichloromethoxy, dibromomethoxy, trifluoromethoxy, trichloromethoxy, tribromomethoxy, 1,1,1-trifluoroethoxy, pentafluoroethoxy, and heptafluoroisopropoxy; alkylthiocarbonyl (preferably C1-6 alkylthiocarbonyl) such as methylthiocarbonyl, ethylthiocarbonyl, propylthiocarbonyl, isopropylcarbonyl, n-butylthiocarbonyl, isobutylthiocarbonyl, s-butylthiocarbonyl, and t-butylthiocarbonyl; alkylsulfonylamino (preferably C1-6 alkylsulfonylamino) such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, isopropylsulfonylamino, n-butylsulfonylamino, and t-butylsulfonylamino; arylsulfonylamino (preferably C6-12 arylsulfonylamino) such as phenylsulfonylamino; heteroarylsulfonylamino (preferably C3-12 heteroarylsulfonylamino) such as piperadinylsulfonylamino; alkylcarbonylamino (preferably C1-6 alkylcarbonylamino) such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, and isopropylcarbonylamino; alkoxycarbonylamino (preferably C1-6 alkoxycarbonylamino) such as methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, and isopropoxycarbonylamino; haloalkylsulfonylamino (preferably C1-6 haloalkylsulfonylamino) such as fluoromethylsulfonylamino, chloromethylsulfonylamino, bromomethylsulfonylamino, difluoromethylsulfonylamino, dichloromethylsulfonylamino, difluoroethylsulfonylamino, trifluoromethylsulfonylamino, 1,1,1-trifluoroethylsulfonylamino, and pentafluoromethylsulfonylamino; bis(alkylsulfonyl)amino (preferably bis(C1-6 alkylsulfonyl)amino) such as bis(methylsulfonyl)amino, bis(ethylsulfonyl)amino, (ethylsulfonyl) (methylsulfonyl)amino, bis(propylsulfonyl)amino, bis(isopropylsulfonyl)amino, bis(n-butylsulfonyl)amino, and bis(t-butylsulfonyl)amino; bis(haloalkylsulfonyl)amino (preferably bis(C1-6 haloalkylsulfonyl)amino) such as bis(fluoromethylsulfonyl)amino, bis(chloromethylsulfonyl)amino, bis(bromomethylsulfonyl)amino, bis(difluoromethylsulfonyl)amino, bis(dichloromethylsulfonyl)amino, bis(difluoroethylsulfonyl)amino, bis(trifluoromethylsulfonyl)amino, bis(1,1,1-trifluoroethylsulfonyl)amino, and bis(pentafluoroethylsulfonyl)amino; unsubstituted or substituted hydrazinomethoxycarbonyl such as hydrazino, N′-phenylhydrazino, and N′-methoxycarbonylhydrazino; alkoxycarbonyl (preferably C1-6 alkoxycarbonyl) such as ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and t-butoxycarbonyl; aryl (preferably C6-12 aryl) such as phenyl, 1-naphthyl, and 2-naphthyl; aralkyl (preferably C7-20 aralkyl) such as benzyl, and phenethyl; unsaturated 5-membered heterocycle such as furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, and 1,2,4-triazol-5-yl; unsaturated 5-membered heterocycle alkyl such as 5-phenyl-5-trifluoromethyl-isoxazolin-3-yl, 2-furfurylmethyl, 3-thienylmethyl, 1-methyl-3-pyrazolomethyl; unsaturated 6-membered heterocycle such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrazin-2-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; unsaturated 6-membered heterocycle alkyl such as 2-pyridylmethyl, 3-pyridylmethyl, 6-chlor-3-pyridylmethyl, and 2-pyrimidylmethyl; saturated heterocyclic group such as tetrahydrofuran-2-yl, tetrahydrapyran-4-yl, piperidin-3-yl, pyrrolidin-2-yl, morpholino, piperidino, and N-methylpiperazinyl; saturated heterocyclic alkyl group such as 2-tetrahydrafuranylmethyl, 3-piperazylmethyl, N-methyl-3-pyrrolidylmethyl, and morpholinomethyl; N-unsubstituted- or N-substituted iminoalkyl such as N-dimethylaminoiminomethyl, 1-N-phenyliminoethyl, N-hydroxyiminomethyl, and N-methoxyiminomethyl; N-unsubstituted- or N-substituted hydrazinocarbonyl such as N′-methylhydrazinocarbonyl, N′-phenylhydrazinocarbonyl, and hydrazinocarbonyl; N-unsubstituted- or N-substituted aminocarbonyl such as aminocarbonyl, dimethylaminocarbonyl, and N-phenyl-N-methylaminocarbonyl; N-unsubstituted- or N-substituted hydrazino such as hydrazino, N′-acetylhydrazino, N′-methylhydrazino, N′-phenylhydrazino, N′-methoxycarbonylhydrazino, and N′-2-propylidenehydrazino; alkylthio such as methylthio, ethylthio, and t-butylthio; alkenylthio such as vinylthio and allylthio; alkynylthio such as ethynylthio and propargylthio; arylthio such as phenylthio, and 4-chlorophenylthio; heteroarylthio such as 2-pyridylthio; aralkylthio such as benzylthio and phenethylthio; alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, and t-butylsulfonyl; alkenylsulfonyl such as allylsulfonyl; alkynylsulfonyl such as propargylsulfonyl; arylsulfonyl such as phenylsulfonyl; heteroarylsulfonyl such as 2-pyridylsulfonyl and 3-pyridylsulfonyl; aralkylsulfonyl such as benzylsulfonyl; and functional groups represented by the formula (i). By associating two or more substituents listed above by substituting one substituent onto another, the resulting substituent can be used in a similar manner as a new substituent.
Specific examples of hydrocarbons in the formula (1) include alkyl such as methyl, ethyl, isopropyl, n-propyl, n-hexyl, and n-octyl; alkenyl such as vinyl, allyl, 1-propenyl, and 2-phenylethenyl; alkynyl such as ethynyl and propargyl; and aromatic hydrocarbon such as phenyl, 1-naphthyl, and 9-anthracel. Specific examples of heterocyclic groups include unsaturated 5-membered heterocycle such as furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, and 1,2,4-triazol-5-yl; unsaturated 5-membered heterocycle alkyl such as 5-phenyl-5-trifluoromethylisoxazolin-3-yl, 2-furfurylmethyl, 3-thienylmethyl, and 1-methyl-3-pyrazolomethyl; unsaturated 6-membered heterocycle such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrazin-2-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; unsaturated 6-membered heterocycle alkyl such as 2-pyridylmethyl, 3-pyridylmethyl, and 6-chlor-3-pyridylmethyl; and saturated heterocycle such as tetrahydrofuran-2-yl, tetrahydrapyran-4-yl, piperidin-3-yl, pyrrolidin-2-yl, morpholino, piperidino, and N-methylpiperazinyl; saturated heterocycle alkyl such as 2-tetrahydrafuranylmethyl, 3-piperazylmethyl, N-methyl-3-pyrrolidylmethyl, and morpholinomethyl. Specific examples of hydrocarbonoxy and hydrocarbonthio include methoxy, ethoxy, isopropoxy, phenoxy, benzyloxy, 2-pyridyloxy, methylthio, ethylthio, phenylthio, benzylthio, and 2-pyridylthio. Specific examples of substituents of functional groups present in R6 and R7 include the same as those shown as specific examples of the substituents of Cy1. Specific examples of functional groups represented by the formula (i) include the functional groups represented by the formulae below.




Y1 and Y2 each independently represents nitrogen or carbon.
X represents oxygen; sulfur; unsubstituted nitrogen or nitrogen substituted with the same substituents as those listed as specific examples of the substituents of Cy1; sulfinyl; or sulfonyl and oxygen is particularly preferable.
Each R may form saturated rings together and the bonding of those at second and sixth positions and at third and fifth positions of the piperidine ring to form saturated rings is preferable and the number of atoms at the cross-linking site, which forms the saturated ring, is preferably 2 or 3. In addition, elements which constitute the cross-linking site of the saturated ring are not particularly limited as long as they are within a chemically acceptable range and specific examples thereof include carbon, oxygen, sulfur, nitrogen, or silicon and the saturated rings can be constituted by combining 2 or more of these elements within a chemically acceptable range. Moreover, each atom can have hydrogen or substituents within the chemically acceptable range thereon and R1a and R2a, R1a and R4a, R2a and R3a, or R3a and R4a may bind oxygen, sulfur, or nitrogen via a double bond within a chemically acceptable range to form carbonyl, thiocarbonyl, imino, or the like.
R which does not form the aforementioned saturated rings together each independently represents hydrogen, halogen, unsubstituted or substituted amino, nitro, hydroxyl, or an organic group. Specific examples of the organic group include cyano; formyl; alkyl, alkoxycarbonyl, alkoxy, haloalkyl, haloalkoxy, alkylthiocarbonyl, alkylsulfonylamino, haloalkylsulfonylamino, bis(alkylsulfonyl)amino, bis(haloalkylsulfonyl)amino, alkoxycarbonyl, and aryl. Alkyl, alkoxycarbonyl, and alkoxy are preferable as the organic group and C1-6 alkyl, C1-6 alkoxycarbonyl, and C1-6 alkoxy are more preferable. Specific examples thereof include the same as those shown as a part of specific examples of the substituents of Cy1.
n is an integer from 0 to 9 and each R may be the same or different when n is 2 or more.
Moreover, each R may bond to form a ring and the number of atoms at the cross-linking site, which forms the saturated ring, is preferably 2 or 3.
Cy2 represents unsubstituted or substituted cyclic hydrocarbon, or unsubstituted or substituted heterocycle. Specific examples thereof include aromatic hydrocarbons such as phenyl, naphthyl-1-yl, and naphthyl-2-yl; and heteroaromatic rings such as furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrazin-2-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; and pyridazin-3-yl is preferable. Specific examples of the non-aromatic rings include cycloalkyl such as cyclopropyl, cyclobutyl, and cyclopentyl; and saturated heterocycle such as piperidino, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-piperazinyl, 3-piperazinyl, and 4-piperazinyl and pyridazin-3-yl is particularly preferable.
Specific examples of the substituents of Cy2 include substituents the same as the specific examples of the substituents of Cy1. It is with a proviso that Cy2 is a pyridin-2-yl which is substituted with one or more cyano when Cy1 is an unsubstituted or substituted phenyl and Cy2 is an substituted pyridin-2-yl. Cy2 does not include unsubstituted pyridin-2-yl, when Cy1 is an unsubstituted or substituted phenyl. The pyridin-2-yl which is substituted with one cyano may have a substituent other than cyano.
II. Novel Cyclic Amine Compounds Represented by the Formula (2)
In the novel cyclic amine compounds represented by the formula (2) (which may hereinafter be referred to as the “compound (2)”), Cy3 is a functional group represented by any one of the formulae (b) to (h).
In the formula (b), specific examples of R6 include substituents the same as a part of the specific examples of the substituents of Cy1.
Specific examples of R7 in formula (c) include alkoxy (particularly preferably C1-6 alkoxy) and alkoxycarbonyl (particularly preferably C1-6 alkoxycarbonyl) which are the same as part of the specific examples of the substituents of Cy1, a functional group represented by the formula (1), which is the same as above; and alkoxyalkyl (particularly preferably C1-6 alkoxy C1-6 alkyl) such as methoxymethyl, ethoxymethyl, propoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 1-propoxyethyl, 2-propoxyethyl, 1-methoxypropyl, 2-methoxypropyl, and 3-methoxypropyl.
Specific examples of R8 to R14 include those the same as part of the specific examples of the substituents of Cy1.
Specific examples of G1, which may be a substituent of a part of R8 to R14, include those the same as part of the specific examples of the substituents of Cy1.
Specific examples of the substituents of nitrogen include those the same as the specific examples of the substituents of Cy1 when X is optionally substituted nitrogen.
Moreover, R1a and R2a, R1a and R4a, R2a and R3a, or R3a and R4a may form saturated rings together and it is preferable that R1a and R2a or R3a and R4a come together to form a ring when forming saturated rings and the number of atoms at the cross-linking site, which forms the saturated ring, is preferably 2 or 3. In addition, elements which constitute the cross-linking site of the saturated ring are not particularly limited as long as they are within a chemically acceptable range and specific examples thereof include carbon, oxygen, sulfur, nitrogen, or silicon and the saturated rings can be constituted by combining 2 or more of these elements within a chemically acceptable range. Moreover, each atom can have hydrogen or substituents within the chemically acceptable range thereon and R1a and R2a, R1a and R4a, R2a and R3a, or R3a and R4a may bind oxygen, sulfur, or nitrogen via a double bond within a chemically acceptable range to form carbonyl, thiocarbonyl, imino, or the like.
R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, and R5 which do not form the aforementioned saturated rings together each independently represents hydrogen, halogen, unsubstituted or substituted amino, nitro, hydroxyl, or an organic group. The organic group represents functional groups generally which contain carbon and the specific examples thereof include cyano; formyl; alkyl; alkoxycarbonyl; alkoxy; haloalkyl, haloalkoxy; alkylthiocarbonyl; alkylsulfonylamino; haloalkylsulfonylamino; bis(alkylsulfonyl)amino; bis(haloalkylsulfonyl)amino; alkoxycarbonyl; and aryl. Alkyl, alkoxycarbonyl, and alkoxy are preferable as the organic group and C1-6 alkyl, C1-6 alkoxycarbonyl, and C1-6 alkoxy are more preferable. Furthermore, specific examples thereof include the same as those shown as a part of specific examples of the substituents of Cy1.
A part of specific examples of G2 in Cy4 include those the same as part of the specific examples of the substituents of Cy1. Specific examples of hydrocarbons commonly present in R17 to R22 in the formulae (j) to (l) in G2 include alkyl such as methyl, ethyl, isopropyl, n-propyl, n-hexyl, and n-octyl; alkenyl such as vinyl, allyl, 1-propenyl, and 2-phenylethenyl; alkynyl such as ethynyl and propargyl; and aromatic hydrocarbon such as phenyl, 1-naphthyl, and 9-anthracel.
Specific examples of heterocyclic groups commonly present in R17, R18, R19, R21, and R22 include unsaturated 5-membered heterocycle such as furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 5-phenyl-5-trifluoromethyl-isoxazolin-3-yl; unsaturated 5-membered heterocycle alkyl such as 2-furfurylmethyl, 3-thienylmethyl, and 1-methyl-3-pyrazolomethyl; unsaturated 6-membered heterocycle such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrazin-2-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl; unsaturated 6-membered heterocycle alkyl such as 2-pyridylmethyl, 3-pyridylmethyl, 6-chlor-3-pyridylmethyl, and 2-pyrimidylmethyl; and saturated heterocycle such as tetrahydrofuran-2-yl, tetrahydrapyran-4-yl, piperidin-3-yl, pyrrolidin-2-yl, morpholino, piperidino, N-methylpiperazinyl; saturated heterocycle alkyl such as 2-tetrahydrafuranylmethyl, 3-piperazylmethyl, N-methyl-3-pyrrolidylmethyl, and morpholinomethyl. Specific examples of hydrocarbonoxy and hydrocarbonthio commonly present in R17 and R18 include methoxy, ethoxy, isopropoxy, phenoxy, benzyloxy, 2-pyridyloxy, methylthio, ethylthio, phenylthio, benzylthio, and 2-pyridylthio. Specific examples of substituents of functional groups present in R17 to R22 include the same as those shown as specific examples of the substituents of Cy1. Y and Z each independently represent oxygen, or unsubstituted or substituted nitrogen and specific examples of a substituent on nitrogen include the same as those shown as specific examples of the substituents of Cy1.
Specific examples of G3 as a substituent of alkyl and alkoxy in G2 include hydroxyl; cyano; alkoxy (preferably C1-6 alkoxy) the same as the specific examples of the substituents of Cy1; alkoxyalkoxy (preferably C1-6 alkoxy C1-6 alkoxy) such as methoxymethoxy, ethoxymethoxy, and propoxyethoxy; and trialkylsilyloxy (preferably tri-C1-6 alkylsilyloxy) such as trimethylsilyloxy, triisopropylsilyloxy, and diisopropylmethylsilyloxy.
Specific examples of the formulae (j) to (l) include the formulae shown below.




As N-oxides of the compounds represented by the formulae (1) and (2), the compounds where nitrogen in the cyclic amine parts or nitrogen in the nitrogen-containing heterocycle of the compounds represented by the formulae (1) and (2) is oxidized, or the like can be shown as examples.
Moreover, examples of salts of the compounds represented by the formulae (1) and (2) include salts of inorganic acids such as hydrochloride salts, nitrate salts, sulfate salts, and phosphate salts; and salts of organic acids such as acetate salts, lactate salts, propionate salts, and benzoate salts.
III. (Production Method)
The production method of the compounds (1) and (2) will be described next.
It should be noted that although the description is provided below by taking the compound (2) as an example, the compound (1) can also be produced in a similar way as that of the compound (2).
1) When X is Oxygen or Optionally Oxidized Sulfur
The compound (2) can be obtained by, for example, subjecting the compound represented by the formula (3) (hereinafter referred to as the “compound (3)) to general deprotection and coupling as shown below.




(In the formula, Cy3, Cy4, X, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, and R5 are the same as above. X′ represents a leaving group such as halogen and R′ represents a protecting group.)

The compound (3), which is an intermediate during the production, can be produced by general reaction as described next.




(In the formula, Cy3, X, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, R5 and R′ are the same as above. X1 and X2 each independently represents hydroxyl or mercapto and X3 represents a leaving group such as halogen.)

Moreover, the compound (2) can also be produced by the general method shown below.




(In the formula, Cy3, Cy4, X, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, and R5 are the same as above. X4 represents a leaving group such as halogen and X5 represents hydroxyl or mercapto.)

The compound (10), which will be a raw material, can be produced by the general reaction shown in the below reaction formula (IV).




(In the formula, Cy4, X4, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, and R5 are the same as above. X6 represents a leaving group such as halogen.)

2) When X is Optionally Substituted Nitrogen

The compounds represented by the formula (16) (hereinafter referred to as the “compound (16)”) can be produced by the general method as shown in the below reaction formula (V).




(In the formula, Cy3, Cy4, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b and R5 are the same as above. R′′ represents a substituent on nitrogen such as hydrogen, trifluoroacetyl, or trifluoromethylsulfonyl.)

The compound (16) which is a compound of the present invention can also be produced by the general reaction as shown in the below reaction formula (VI).





(In the formula, Cy3, Cy4, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, R5, and R′′ are the same as above. X7 represents a leaving group such as halogen and sulfonyloxy.)

The compound (16) which is a compound of the present invention can also be produced by the general coupling reaction as shown in the below reaction formula (VII).





(In the formula, Cy3, Cy4, R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, R5, R′′ and X7 are the same as above.)

IV. Agents for Pest Control Characterized by Containing the Cyclic Amine Compounds Represented by the Formula (1) or (2), Salts Thereof, or N-Oxides Thereof, as Active Ingredients

The compounds of the present invention (the compounds represented by the formulae (1) and (2), salts thereof, or N-oxides thereof) have excellent adulticidal, nymphicidal, larvicidal, or ovicidal activities and can be used for controlling pests in agriculture, sanitary insects, stored grain pest insects, clothes pests, household pests, or the like. Representative examples thereof include the following.
Pests which belong to the order of Lepidoptera such as Spodoptera litura, Mamestra brassicae, Agrotis ipsilon, green caterpillars, Autographa nigrisigna, Plutella xylostella, Adoxophyes honmai, Homona magnanima, Carposina sasakii, Grapholita molesta, Phyllocnistis citrella, Caloptilia theivora, Phyllonorycter ringoniella, Lymantria dispar, Euproctis pseudoconspersa, Chilo suppressalis, Cnaphalocrocis medinalis, Ostrinia nubilasis, Hyphantria cunea, Cadra cautella, genus Heliothis, genus Helicoverpa, genus Agrothis, Tinea translucens, Cydia pomonella, and Pectinophora gossypiella; 
pests which belong to the order of Hemiptera such as Myzus persicae, Aphis gossypii, Lipaphis erysimi, Rhopalosiphum padi, Riptortus clavatus, Nezara antennata, Unaspis yanonensis, Pseudococcus comstocki, Trialeurodes vaporariorum, Bemisia tabaci, Bemisia argentifolii, Psyllapyrisuga, Stephanitis nashi, Nilaparuata lugens, Laodelphax stratella, Sogatella furcifera, and Nephotettix cincticeps; 
pests which belong to the order of Coleoptera such as Phyllotreta striolata, Aulacophora femoralis, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Sitophilis zeamais, Callosobruchus chinensis, Popilliajaponica, Anomala rufocuprea, genus Diabrotica, Lasioderma serricorne, Lyctus brunneus, Monochamus alternatus, Anoplophora malasiaca, genus Agriotis, Epilachna vigintioctopunctata, Tenebroides mauritanicus, and Anthonomus grandis; 
pests which belong to the order of Diptera such as Musca domestica, Calliphora lata, Boettcherisca peregrine, Zeugodacus cucurbitae, Bactrocera dorsalis, Delia platura, Agromyza oryzae, Drosophila melanogaster, Stomoxys calcitrans, Culex tritaeniorhynchus, Aedes aegypti, and Anopheles sinensis; 
pests which belong to the order of Thysanoptera such as Thrips palmi and Scirtothrips dorsalis; 
pests which belong to the order of Hymenoptera such as Monomorium pharaonis, Vespa simillima xanthoptera, and Athalia rosae ruficornis; 
pests which belong to the order of Orthoptera such as Locusta migratoria, Blattella germanica, Periplaneta americana, and Periplaneta fuliginosa; 
pests which belong to the order of Isoptera such as Coptotermes formosanus and Reticulitermes speratus speratus; 
pests which belong to the order of Siphonaptera such as Pulex irritans and Ctenocephalides felis felis; 
pests which belong to the order of Phthiraptera such as Pediculus humanus; Acarina such as Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus kanzawai, Panonychus citri, Panonychus ulmi, Aculopspelekassi, Aculus schlechtendali, Polyphagotarsonemus latus, genus Brevipalpus, genus Eotetranichus, Rhizoglyphus robini, Tyrophagus putrescentiae, Dermatophagoides farinae, Boophilus microplus, and Haemaphysalis longicornis; and
plant parasitic nematodes such as Meloidogyne incognita, Pratylenchus spp., Heterodera glycines, Aphelenchoides besseyi, and Bursaphelenchus xylophilus. 
Pests to which the present invention is preferably applied are pests which belong to the order of Lepidoptera, pests which belong to the order of Hemiptera, Acarina, pests which belong to the order of Thysanoptera, and pests which belong to the order of Coleoptera, and particularly preferably Acarina.
Moreover, drugs which are also effective for pests or Acarnia that are of resistant lineage are desired because in recent years, resistance to organophosphorus pesticides, carbamate pesticides, or acaricides developed among many pests such as Plutella xylostella, Delphacidae, Deltocephalidae, and Aphididae has caused problems because of insufficient effects of these drugs. The compounds of the present invention are drugs having excellent insecticidal and acaricidal effects not only on those of sensitive lineages but also on pests of lineages resistant to organophosphorus pesticides, carbamate pesticides, and pyrethroid pesticides, and on Acarnia of lineages resistant to acaricides.
The compounds of the present invention are drugs that show less herbicide injuries, have lower toxicity to fish and warm-blooded animals, and with higher safety.
The compounds of the present invention can also be used as an antifoulant to prevent aquatic organisms attaching to objects which contact water such as ship bottoms and fishing nets.
Moreover, some of the compounds of the present invention exhibit microbiocidal activities, herbicidal activities, or plant-growth regulating activities. Furthermore, some intermediates of the compounds of the present invention exhibit insecticidal/acaricidal activities.
Although the compounds of the present invention are, needless to say, sufficiently effective even when used solely, they can also be used by mixing or combining with one or more of other agents for pest control, germicides, insecticides/acaricides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feed, or the like.
Representative examples of active ingredients of germicides, acaricides, plant growth regulators, or the like which can be used by mixing or combining with the compounds of the present invention are shown below.
Germicides:
captan, folpet, thiuram, ziram, zineb, maneb, mancozeb, propineb, polycarbamate, chlorothalonin, quintozene, captafol, iprodione, procymidone, fluoroimide, mepronil, flutolanil, pencycuron, oxycarboxin, fosetyl-aluminum, propamocarb, triadirnefon, triadimenol, propiconazole, diclobutrazol, bitertanol, hexaconazole, myclobutanil, flusilazole, etaconazole, fluotrimazole, flutriafen, penconazole, diniconazole, cyproconazole, fenarimol, triflumizole, prochloraz, imazalil, pefurazoate, tridemorph, fenpropimorph, triforine, buthiobate, pyrifenox, anirazine, polyoxins, metalaxyl, oxadixyl, furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate-methyl, hymexazol, basic copper chloride, basic copper sulfate, fentinacetate, triphenyltin hydroxide, diethofencarb, chinomethionat, binapacryl, lecithin, baking soda, dithianon, dinocap, fenaminosulf, diclomezine, guazatine, dodine, IBP, edifenphos, mepanipyrim, fermzone, trichlamide, methasulfocarb, fluazinam, ethoquinolac, dimethomorph, pyroquilon, tecloftalam, phthalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, cymoxanil, cyclobutanil, guazatine, propamocarb hydrochloride, oxolinic acid, cyflufenamid, iminoctadine, kresoxim-methyl, triazine, fenhexamid, cyazofamid, cyprodinil, prothioconazole, fenbuconazole, trifloxystrobin, azoxystrobin, hexaconazole, imibenconazole, tebuconazole, difenoconazole, and carpropamid;
Insecticides/acaricides:
organophosphorus and carbamate pesticides:
fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, vamidothion, phenthoate, dimethoate, formothion, malathion, trichlorphon, thiometon, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydemeton methyl, ethion, salithion, cyanophos, isoxathion, pyridafenthion, phosalone, methidathion, sulprofos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenofos, pyraclofos, monocrotophos, azinphos-methyl, aldicarb, methomyl, thiodicarb, carbofuran, carbosulfan, benfuracarb, furathiocarb, propoxur, BPMC, MTMC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, cartap, thiocyclam, bensultap, and the like; pyrethroid pesticides:
permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propathrin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, etofenprox, cycloprothrin, tralomethrin, silafluofen, and acrinathrin;
Benzoylurea and other Pesticides:
diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiuron, imidacloprid, fipronil, nicotine sulfate, rotenone, metaldehyde, acetamiprid, chlorfenapyr, nitenpyram, thiacloprid, clothianidin, thiamethoxam, dinotefuran, indoxacarb, pymetrozine, spinosad, emamectin, pyridalyl, tebufenozide, chromafenozide, methoxyfenozide, tolfenpyrad, machine oil, microbial pesticides such as BT and entomopathogenic viruses;
Nematicides:
fenamiphos, fosthiazate, cadusafos, and the like;
Acaricides:
chlorobenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexythiazox, fenbutatin oxide, polynactin, chinomethionat, CPCBS, tetradifon, avermectin, milbemectin, clofentezine, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, fenothiocarb, dienochlor, fluacrypyrim, acequinocyl, bifenazate, etoxazole, spirodiclofen, fenazaquin, and the like; plant growth regulators:
gibberellins (for example, gibberellin A3, gibberellin A4, or gibberellin A7), IAA, NAA, or the like.
Agents for pest control of the present invention contain one or more compounds of the present invention as an active ingredient.
Although the compounds of the present invention can be used as they are without adding any other components as agents for pest control, they can be formulated for use. In other words, by mixing at least one of the compounds of the present invention with solid, liquid, or gaseous carriers, or by impregnating at least one of the compounds of the present invention in substrates such as porous ceramic plates and nonwoven fabrics, and by adding surfactants or other adjuvants where necessary, the compounds are formulated, with the objective to use as agrochemicals, into the form which general agrochemicals may adopt and can be used.
Examples of agrochemical formulations include wettable powder, granule, dusting powder, emulsion, water-soluble powder, suspending agent, granulated wettable powder, floable, aerosol, transpiration agent by heating, fumigant, poison bait, microcapsule, or the like.
As additives and carriers, vegetable powders such as soy flour and wheat flour; fine mineral powder such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, and clay; and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used when solid formulation is required. When liquid form of formulation is required, petroleum fractions such as kerosene, xylene, and solvent naphtha, and cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, methyl isobutyl ketone, mineral oil, vegetable oil, water, or the like are used as a solvent. As gaseous carriers used in propellant, butane (gas), LPG, dimethyl ether, and carbon dioxide gas can be used.
As a substrate of poison bait, bait components such as grain powder, vegetable oil, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives such as dehydroacetic acid; agents for preventing accidental ingestion by children or pets such as capsicum powder; and pest-insect attracting scents such as cheese scents and onion scents can be used.
Additionally, in order to achieve homogenous and stable forms in these formulations, it is also possible to add surfactants if necessary. Although surfactants are not particularly limited, examples thereof include, for instance, nonionic surfactants such as alkyl ether where polyoxyethylene is added, higher fatty acid ester where polyoxyethylene is added, sorbitan higher fatty acid ester where polyoxyethylene is added, and tristyryl phenyl ether where polyoxyethylene is added; sulfate ester salt of alkyl phenyl ether where polyoxyethylene is added, alkyl naphthalene sulfonate salt, polycarboxylate salt, lignin sulfonate salt, formaldehyde condensate of alkyl naphthalene sulfonate, and isobutylene-maleic anhydride copolymer.
When the compounds of the present invention are used as agents for pest control in agriculture, the amount of active ingredient in the formulation is 0.01 to 90 weight % and particularly preferably 0.05 to 85 weight % and wettable powder, emulsion, suspending agents, floable agents, water-soluble powder, granulated wettable powder which are diluted to predetermined concentrations with water, and dusting powder and granules as they are, are applied onto plants or soil.
In addition, when the compounds of the present invention are used as agents for pest control in quarantine purposes, emulsion, wettable powder, floable agents, and the like are applied by diluting to predetermined concentrations with water and oil solution, aerosol, poison bait, anti-acarid sheet, and the like are applied as they are.
When the compounds of the present invention are used as agents for pest control in controlling ectoparasites of livestock such as cattle and pigs or of pets such as dogs and cats, formulations using the compounds of the present invention are used in known methods in the field of veterinary medicine. As such methods, examples thereof include a method for administering in forms such as tablets, capsules, immersion liquid, feedstuff mix, suppository, and injection (intramuscular, subcutaneous, intravenous, intraperitoneal, or the like) when systemic control is required and a method for administering by spraying, pouring-on, or spotting-on oily- or aqueous liquid formulations or a method for mounting objects, which are resin formulations shaped into collars, ear tags, or the like, when non-systemic control is required. In this case, the proportion is normally used where 0.01 to 1000 mg of the compounds of the present invention are applied per 1 kg of host animal.
EXAMPLE
Next, the present invention will be described in further detail by using Examples. However, the present invention is not limited to the Examples below in any aspects.
Production Example 1
Production of 8β-[2-isopropylideneaminooxy-4-(trifluoromethyl)phenoxy]-3-(5-cyano-pyridin-2-yl)-3-azabicyclo[3.2.1]octane (E)
Step 1
Production of 8β-hydroxy-3-(5-cyano-pyridin-2-yl)-3-azabicyclo[3.2.1]octane (A)




5 ml of acetonitrile suspension containing 0.15 g of 3-azabicyclo[3.2.1]octa-8-ol, 0.65 g of potassium carbonate, and 0.33 g of 2-chloro-5-cyanopyridine was refluxed with heating overnight. After being cooled to room temperature, the mixture was poured into water and extracted with ethyl acetate. Organic layer was washed with saline and dried with anhydrous magnesium sulfate. 0.16 g of a crude compound (A) was obtained by evaporating solvents under reduced pressure and this compound was directly used in the next step.
Step 2
Production of 8β-[2-methoxymethoxy-4-(trifluoromethyl)phenoxy]-3-(5-cyano-pyridine-2-yl)-3-azabicyclo[3.2.1]octane (B)




0.14 g of 60% sodium hydride was added to 10 ml of dimethylformamide (DMF) solution containing 0.58 g of 4-fluoro-3-hydroxybenzotrifluoride with ice-cooling. After stirring the mixture for 30 minutes at room temperature, 0.28 g of chloromethyl ether was added dropwise thereto with ice-cooling. After completing the addition, the reaction solution was heated to room temperature and stirred for 30 minutes and then further heated to 80° C. and stirred for 30 minutes. 0.49 g of the compound (A) and 0.13 g of 60% sodium hydride were added to the reaction mixture at 80° C. and the resulting mixture was stirred for 30 minutes and then heated to 80° C. and was further stirred for 2 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. After being washed with water and dried with anhydrous magnesium sulfate, the organic layer was filtered and evaporated under reduces pressure. The concentrate was purified by silica gel column chromatography (eluant: mixed solvent of n-hexane and ethyl acetate) to obtain 0.82 g of the target compound (B).
1H-NMR(CDCl3, δppm):1.55-1.63(m, 2H), 2.02-2.05(m, 2H), 2.60(brs, 2H), 3.13(d, 2H), 3.52(s, 3H), 4.22(d, 2H), 4.63(s, 1H), 5.20(s, 2H), 6.58(d, 1H), 7.03(d, 1H), 7.26(d, 1H), 7.37(s, 1H), 7.62(d, 1H), 8.41(s, 1H)Step 3
Production of 8β-[2-hydroxy-4-(trifluoromethyl)phenoxy]-3-(5-cyano-pyridine-2-yl)-3-azabicyclo[3.2.1]octane (C)




10 ml of 10% hydrochloric acid was added to 10 ml of tetrahydrofuran (THF) solution containing 0.82 g of the compound (B) at room temperature. The mixture was refluxed with heating for 30 minutes, poured into water, and extracted with ethyl acetate. The organic layer was washed with saline and dried with anhydrous magnesium sulfate. 0.74 g of the target compound (C) was obtained by evaporating the solvents under reduced pressure. This compound was directly used in the next step without purification.
1H-NMR(CDCl3, δppm):1.62-1.75(m, 2H), 1.91-1.98(m, 2H), 2.65(brs, 2H), 3.17(d, 2H), 4.26(d, 2H), 4.66(s, 1H), 5.63(s, 1H), 6.60(d, 1H), 6.98(d, 1H), 7.13(d, 1H), 7.16(s, 1H), 7.63(d, 1H), 8.42(s, 1H)
Step 4
Production of 8β-[2-isopropylideneaminooxy-4-(trifluoromethyl)phenoxy]-3-(5-cyano-pyridine-2-yl)-3-azabicyclo[3.2.1]octane (E)




0.76 g of a compound (D) was synthesized by the method described in Japanese Patent Application Laid-Open No. 2001-81071 using 0.74 g of the compound (C).
1H-NMR(CDCl3, δppm):1.55-1.68(m, 2H), 1.99-2.04(m, 2H), 2.59(brs, 2H), 3.13(d, 2H), 4.22(d, 2H), 4.60(s, 1H), 6.00(brs, 2H), 6.59(d, 1H), 6.98(d, 1H), 7.20(d, 1H), 7.60(d, 2H), 8.01(s, 1H), 8.41(s, 1H)
3 ml of acetone and 1 drop of concentrated hydrochloric acid were added to 3 ml of ethanol solution containing 0.76 g of the compound (D) and the entire mixture was stirred for 1 hour at room temperature. The mixture was poured into water and extracted with ethyl acetate. After being washed with water and dried with anhydrous magnesium sulfate, the organic layer was filtered and then vacuum-concentrated. The concentrate was purified by silica gel column chromatography (eluant: mixed solvent of n-hexane and ethyl acetate) to obtain 0.45 g of the target compound (E). Melting temperature: 120-122° C.
Production Example 2
Production of cis-3-methyl-4-[2-propoxy-4-(trifluoromethyl)phenoxy]-1-[6-(trifluoromethyl)-pyridazin-3-yl]piperidine and
trans-3-methyl-4-[2-propoxy-4-(trifluoromethyl)phenoxy]-1-[6-(trifluoromethyl)-pyridazin-3-yl]piperidine
Step 1
Production of trans-1-benzyl-3-methyl-4-[2-propoxy-4-(trifluoromethyl)phenoxy]piperidine (Htrans) and cis-1-benzyl-3-methyl-4-[2-propoxy-4-(trifluoromethyl)phenoxy]piperidine (Hcis)




0.47 g of sodium borohydride was added to 40 ml of ethanol solution containing 2.53 g of N-benzyl-3-methyl-4-piperidinone (F) with ice-cooling. The mixture was stirred for 2 hours at room temperature and then neutralized with 10% hydrochloric acid with ice-cooling. The resulting mixture was extracted with methylene chloride and the organic layer was dried with anhydrous magnesium sulfate. 2.27 g of a crude compound (G) was obtained by evaporating the solvents under reduced pressure. This compound was directly used in the next reaction.
0.66 g of 4-fluoro-3-propoxybenzotrifluoride was added to 15 ml of DMF containing 1 g of the crude compound (G). The mixture was heated to 80° C. and 0.29 g of 60% sodium hydride was added thereto and the resulting mixture was kept heated for 5 hours at 100° C. The mixture was cooled to room temperature, poured into water, and then extracted with ethyl acetate. After being washed with water and dried with anhydrous magnesium sulfate, the organic layer was filtered and vacuum-concentrated. The concentrate was purified by silica gel column chromatography (eluant: mixed solvent of n-hexane and ethyl acetate) to obtain 0.35 g of a trans isomer (Htrans) and 0.21 g of a cis isomer (Hcis) as first and second fractions, respectively.
Step 2
Production of cis-3-methyl-4-[2-propoxy-4-(trifluoromethyl)phenoxy]-1-[6-(trifluoromethyl)-pyridazin-3-yl]piperidine (Jcis) and
trans-3-methyl-4-[2-propoxy-4-(trifluoromethyl)phenoxy]-1-[6-(trifluoromethyl)-pyridazin-3-yl]piperidine (Jtrans)




0.1 g of 20% palladium hydroxide-carbon was added to 4 ml of ethanol solution containing 0.35 g of the trans isomer (Htrans). This suspension was heated to 60° C. and stirred for 1 day and night under hydrogen atmosphere (hydrogen pressure: 1.01×105 Pa). After cooling the mixture to room temperature, 8 ml of ethanol and 0.1 g of 20% palladium hydroxide-carbon were added thereto. This suspension was heated to 60° C. and stirred for 9 hours under hydrogen atmosphere (hydrogen pressure: 1.01×105 Pa). The mixture was cooled to room temperature and then subjected to celite filtration. 0.22 g of a crude compound (1) was obtained by evaporating the filtrate under reduced pressure. This compound was directly used in the next reaction.
0.14 g of 3-chloro-6-(trifluoromethyl)pyridazine, 0.28 g of potassium carbonate, and 10 mg of tetra-n-butylammonium iodide were added to 2 ml acetonitrile solution containing 0.22 g of the crude compound (I) and the mixture was refluxed with heating for 1 hour at 120° C. The mixture was cooled to room temperature, poured into water, and then extracted with ethyl acetate. After being washed with water, and dried with anhydrous magnesium sulfate, the organic layer was filtered and vacuum-concentrated. The concentrate was purified by silica gel column chromatography (eluant: mixed solvent of n-hexane and ethyl acetate) to obtain 0.2 g of the target compound (Jtrans).
Viscous Oil
1H-NMR data of this compound are as follows.
1H-NMR(CDCl3, δppm):1.04(t, 3H), 1.14(d, 3H), 1.77-1.88(m, 3H), 2.11-2.19(m, 2H), 3.20(dd, 1H), 3.45-3.54(m, 1H), 3.98(t, 2H), 4.16-4.31(m, 3H), 6.97(twod's, 1H×2), 7.10(s, 1H), 7.13(d, 1H), 7.46(d, 1H)
0.16 g of the target compound (Jcis) was obtained from 0.21 g of the cis isomer (Hcis) by a similar process. Viscous oil
1H-NMR data of this compound are as follows.
1H-NMR(CDCl3, δppm):1.06(t, 3H), 1.11(d, 3H), 1.74-1.91(m, 3H), 2.05-2.13(m, 2H), 3.48(dd, 1H), 3.57-3.66(m, 1H), 3.98(t, 2H), 4.09-4.19(m, 2H), 4.56-4.58(m, 1H), 6.97(twod's, 1H×2), 7.10(s, 1H), 7.16(d, 1H), 7.46(d, 1H)
Production Example 3
Production of 3α-(5-trifluoromethyl-2-pyridyloxy)-8-(5-trifluoromethyl-pyridine-2-yl)-8-azabicyclo[3.2.1]octane (N)




23.3 g of 2,2,2-trichloroethyl chloroformate ester was added to 150 ml of the benzene suspension containing 14.1 g of tropine and 1.4 g of potassium carbonate at room temperature and the entire mixture was refluxed for 3.5 hours. After being cooled to room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saline and dried with anhydrous magnesium sulfate. 30.1 g of an oily carbonate (K) was obtained by evaporating the solvents under reduced pressure and this carbonate was used directly in the next reaction.
Next, 65 g of zinc powder was added to 250 ml of the acetate solution of this carbonate (K). After being stirred for 5 minutes, the mixture was heated at 80° C. for 1 hour. After being cooled to room temperature, the mixture was subjected to celite filtration. 15.5 g of a crude product of the compound (L) was obtained by vacuum-concentrating the filtrate.
150 ml of acetonitrile suspension containing 5.64 g of the crude product of the compound (L) obtained as above, 41.5 g of potassium carbonate, and 8.2 g of 2-chloro-5-trifluoromethylpyridine was refluxed for 3.5 hours. After being cooled to room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saline and dried with anhydrous magnesium sulfate. 3.5 g of the compound (M) was obtained as crystals by evaporating the solvents under reduced pressure.
1H-NMR(CDCl3, δ ppm):1.42(d, 1H), 1.77(d, 2H), 2.05-2.20(m, 4H), 2.32-2.39(m, 2H), 4.09(brs, 1H), 4.53(brs, 2H), 6.52(d, 1H), 7.58(dd, 1H), 8.38(d, 1H)
32 mg of 60% sodium hydride was added to 3 ml of DMF solution containing 0.21 g of the compound (M) with ice-cooling and the entire mixture was stirred for 40 minutes. Subsequently, 0.17 g of 2-chloro-5-trifluoromethylpyridine was added to this mixture and the resulting mixture was heated to 100° C. and was stirred overnight with heating. After cooling to room temperature, the reaction mixture was poured into ice-cold water and extracted with ethyl acetate. After being washed with water and dried with anhydrous magnesium sulfate, the organic layer was filtered and then vacuum-concentrated. The residue was purified by column chromatography (developing solution: mixed solvent of n-hexane and ethyl acetate) to obtain the target compound (N). Melting temperature: 104-105° C.
1H-NMR(CDCl3, δppm):1.25(s, 1H), 1.55(s, 1H), 1.95-2.33(m, 6H), 4.58(brs, 2H), 5.37(t, 1H), 6.55(d, 1H), 6.80(d, 1H), 7.61(dd, 1H), 7.78(dd, 1H), 8.41(s, 2H),
Examples of the compounds of the present invention produced by the method according to the above Examples are shown in the Table below including the compounds produced in the above Examples. Note that in the Table below, R1 and R2 show substituents including substituents associated by two or more substituents so that the Table is simplified. Also, the description “vis” shows that the compound is a viscous oil and the description “amor” shows that the compound is amorphous. Moreover, nD21.8-1.5008 means that the refractive index at 21.8° C. is 1.5008 (the same also applies to others). In addition, the description “cPr” means cyclopropyl, the description “cHex” means cyclohexyl (the same also applies to others), the description “Ac” means acetyl, the description “nPr” means normal propyl, the description “iPr” means isopropyl, the description “nBu” means normal butyl, the description “iBu” means isobutyl, and the description “tBu” means tertiary butyl, and the description “TMS” means trimethylsilyl and the description “THF” means tetrahydrofuranyl.







TABLES 1-3













 















Physical






constant


Compound



[ ]: Melting


No.
R2
X
R1
point ° C.





1-1 
5-CF3
O
2-OnPr-4-CF3
[90-92]


1-2 
5-CF3
O
2-CHO-4-CF3
[122-123]


1-3 
5-CF3
O
2-CH2OH-4-CF3
vis


1-4 
5-CF3
O
2-CH2OCH(OMe)Me-4-CF3
[82-85]


1-5 
5-CF3
O
2-CH2OEt-4-CF3
vis


1-6 
5-CF3
O
2-Cl-4-CF3
[92-93]


1-7 
5-CF3
O
2-C(O)OiPr-4-CF3
vis


1-8 
5-CF3
O
2,6-(NO2)2-4-CF3
vis


1-9 
5-CF3
O
2-C(O)NHCH(Me)CH2OH-4-CF3
amor


1-10
5-CF3
O
2-CH═NOEt-4-CF3
vis


1-11
5-CF3
O
(E)-2-CH═NOiPr-4-CF3
[79-80]


1-12
5-CF3
O
2-CH═NO-propargyl-4-CF3
[84-86]


1-13
5-CF3
O
2-(5-Me-oxazoline-2-yl)-4-CF3
vis


1-14
3-Cl-5-CF3
O
2-CH2OEt-4-CF3
vis


1-15
5-CF3
O
2-OMe-4-CF3
[127-130]


1-16
5-CF3
O
(Z)-2-CH═NOiPr-4-CF3
vis


1-17
5-CF3
O
2-C(O)OEt-4-CF3
vis


1-18
5-CF3
O
2-C(O)OtBu-4-CF3
[95-98]


1-19
3-Cl-5-CF3
O
2-C(O)OiPr-4-CF3
vis


1-20
5-CF3
O
6-Cl-2-C(O)OiPr-4-CF3
vis


1-21
5-CF3
O
2-CH═NOMe-4-CF3
vis


1-22
5-CF3
O
2-CH═NOMe-4-CF3
vis


1-23
5-CF3
O
2-C(O)OCH2cPr-4-CF3
vis


1-24
5-CF3
O
2-C(O)OCH2CF3-4-CF3
vis


1-25
5-CF3
O
2-C(O)OiBu-4-CF3
vis


1-26
5-CF3
O
2-C(O)OnPr-4-CF3
vis


1-27
5-CF3
O
2-CH(OH)CH2CH(Me)2-4-CF3
amor


1-28
5-CF3
O
2-C(O)OCH(Me)CH═CH2-4-CF3
vis


1-29
5-CF3
O
2-C(O)OcPen-4-CF3
vis


1-30
5-CF3
O
2-C(O)ON═C(Me)2-4-CF3
vis


1-31
5-CF3
O
2-OCH2cPr-4-CF3
[88-90]


1-32
5-CF3
O
2-OEt-4-CF3
[102-105]


1-33
5-CF3
O
2-C(O)OCH2CHF2-4-CF3
vis


1-34
5-CF3
O
2-OnBu-4-CF3
[90-92]


1-35
5-CF3
O
2-OnPr-4-CN
[107-110]


1-36
5-CF3
O
2-C(O)OCH2OMe-4-CF3
vis


1-37
5-CF3
O
2-C(O)OCH2tBu-4-CF3
[100-102]


1-38
5-CF3
O
2-C(O)N(Me)2-4-CF3
vis


1-39
5-CF3
O
2-C(O)OCH(Me)CH(Me)2-4-CF3
vis


1-40
5-CF3
O
2-C(O)OCH(Et)2-4-CF3
vis


1-41
5-CF3
O
2-C(O)O(THF-3-yl)-4-CF3
vis


1-42
5-CF3
NH
2-C(O)OiPr-4-CF3
vis


1-43
5-CF3
O
2-C(O)O(CH2)2OMe-4-CF3
vis


1-44
5-CF3
O
2-C(O)OCH(Me)CH2OMe-4-CF3
vis


1-45
5-CF3
O
2-C(O)OCH(CN)Me-4-CF3
vis


1-46
5-CF3
O
2-C(O)OCH(Cl)Et-4-CF3
vis


1-47
5-CF3
O
2-C(O)SiPr-4-CF3
vis


1-48
5-CF3
O
2-OBn-4-CF3
 [98-102]


1-49
5-CF3
O
2-OH-4-CF3
[130-131]


1-50
5-CF3
O
2-OCH2CH(Me)OMe-4-CF3
[116-120]


1-51
5-CN
O
2-C(O)OiPr-4-CF3
[124-126]


1-52
5-CF3
O
2-CH(OTMS)CH2CN-4-CF3
[131-133]


1-53
5-CF3
O
2-CH(OH)CH2CN-4-CF3
[24-25]


1-54
5-CN
O
2-OnPr-4-CF3
[141-142]


1-55
5-CF3
O
2-OCH2cPr-4-C3F7
nD22.2-1.4942 


1-56
3-Me
O
4-Ph



1-57
3-F
O
3,4,5,6-F4



1-58
5-CN
S
2-CN



1-59
5-NO2
S
3-CF3



1-60
5-CHO
S
4-iPr



1-61
4-OMe
S
3,5-Me2



1-62
4-cPr
S
3-NO2



1-63
5-OcHex
SO2
3-Br



1-64
3-CH2CH2cPr
SO2
3-cPr



1-65
4-OCH2cPr
SO2
4-OcPr



1-66
4-OCH═CH2
SO2
2-CH2cPr



1-67
5-OCF3
SO2
2-OCH2cPr



1-68
4-OCH═CHCH2CF3
NH
4-OCH═CH2



1-69
4-CO2Et
NH
2-OCH2Cl



1-70
6-F
NH
2-OCH═CBr2



1-71
6-CN
NMe
3-NO2



1-72
6-NO2
NAc
4-OCF3



1-73
6-OcPr
NMe
4-CN
















TABLE 4













 















Physical






constant


Compound



[ ]: Melting


No.
R2
X
R1
point ° C.





2-1
5-CF3
O
4-CF3-6-Cl
nD22.1-1.5134 


2-2
4-CF3-6-Cl
O
5-CF3
vis


2-3
5-CF3
O
5-CF3
[104-105]


2-4
5-CF3-6-OnPr
O
5-CF3
[90-93]


2-5
5-CF3
S
4-cPr



2-6
3-Me
S
3-OcPr



2-7
3-F
S
3,5-Me2



2-8
5-CN
S
4-CF3



2-9
5-NO2
SO2
5-CO2Et



 2-10
5-CHO
SO2
4-CH═CF2



 2-11
4-OMe
SO2
5-CH═Cme2



 2-12
4-cPr
SO2
3-OCH2CH2cPr



 2-13
5-OcHex
NH
4-CH2cPr



 2-14
3-CH2CH2cPr
NH
3-Oet-4-cPr



 2-15
4-OCH2cPr
Nme
4-CHO



 2-16
6-Me
Nme
5-NO2
















TABLE 5













 















Physical


Com-



constant


pound



[ ]: Melting


No.
R2
X
R1
point ° C.





3-1
6-CF3
O
2-C(O)OiPr-4-CF3
[154-157]


3-2
6-CF3
O
2-CH2OEt-5-CF3
nD22.2-1.4996 


3-3
4-CF3
O
2-Me



3-4
5-CF3
O
3-Cl



3-5
4-Br
S
4-CF3



3-6
5-Me
S
3-NO2



3-7
6-CF3
S
3-CO2Me



3-8
6-CF3
SO2
4-tBu



3-9
4-cPr
SO2
3-cPr



 3-10
6-CF3
NH
4-OcHex



 3-11
6-OCH2CH2cPr
NH
4-Nme2



 3-12
5-CH═Cme2
NH
3-iPr



 3-13
6-CF3
Nme
4-OCF3



 3-14
4-NO2
Nme
2-CN



 3-15
5-CHO
Nac
4-CHO
















TABLES 6-9













 
























Physical



Com-







constant



pound







[ ]: Melting



No.
R1
Q1
Q2
Q3
Q4
Q5
X
point ° C.
Remark





4-1 
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[197-199]



4-2 
2-OnPr-4-CF3
N
CH
C—Me
CH
N
O
[175-176]



4-3 
2-OnPr-4-CF3
N
C—Cl
N
CH
C—Me
O
[128-132]



4-4 
2-OnPr-4-CF3
N
C—Cl
C—Me
CH
N
O
 [83-189]



4-5 
2-OnPr-4-CF3
N
CH
C—CF3
CH
N
O
[152-155]



4-6 
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
amor
R3b = R5b = Me


4-7 
2-OCH2CH(Me)OMe-4-CF3
N
N
C—CF3
CH
CH
O
[181-185]



4-8 
2-OCH2cPr-4-CF3
N
N
C—CN
CH
CH
O
[213-215]



4-9 
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
O
[204-206]



4-10
2-CO2iPr-4-CF3
N
N
C—CN
CH
CH
O
[219-221]



4-11
2-OnBu-4-CF3
N
N
C—CF3
CH
CH
O
[197-199]



4-12
2-OiBu-4-CF3
N
N
C—CF3
CH
CH
O
[223-224]



4-13
2-Oet-4-CF3
N
N
C—CF3
CH
CH
O
[192-194]



4-14
2-CO2iPr-4-CF3
N
N
C—CF3
CH
CH
O
[201-203]



4-15
2-OCH2CH(F)Me-4-CF3
N
N
C—CN
CH
CH
O
[214-218]



4-16
2-OCH2CH(F)Me-4-CF3
N
N
C—CF3
CH
CH
O
[197-200]



4-17
2-OCH2cPr-4-CF3
CH
N
C—Cl
CH
CH
O
[148-150]



4-18
2-OCH2cPr-4-CF3
CH
N
C—CN
CH
CH
O
[126-128]



4-19
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[214-216]
sulfate


4-20
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[220up]
borate


4-21
4-CF3
N
N
C—CF3
CH
CH
O
[187-188]



4-22
2-OnPr-4-CF3
CH
N
C—Cl
CH
CH
O
[149-150]



4-23
4-CF3
C—OnPr
N
C—CF3
CH
CH
O
nD21.9-











1.5132



4-24
2-CH2Oet-4-CF3
N
N
C—CF3
CH
CH
O
vis



4-25
4-CF3
CH
CH
N
CH
CH
O




4-26
2,6-Me2
CH
Cme
N
CBr
CH
O




4-27
4-Ome
N
N
Cme
CH
CH
S




4-28
3-NO2
N
N
C—CF3
CH
CH
S




4-29
2-F
N
N
C—CF3
CH
CH
S




4-30
3-CHO
N
N
C—CN
CH
CH
S




4-31
3-OiPr
N
N
C—CF3
CH
CH
S




4-32
4-Me
CH
N
C—Cl
CH
CH
S




4-33
4-cPr
CH
N
C—CN
CH
CH
S




4-34
3-OcPr
N
N
C—CF3
CH
CH
S




4-35
4-CH2cPr
N
N
C—CF3
CH
CH
SO2




4-36
2-OCH2CH2cPr
N
N
C—CF3
CH
CH
SO2




4-37
3-OCH═Cme2
N
N
C—CF3
CH
CH
SO2




4-38
4-OCF3
N
N
C—CF3
CH
CH
SO2




4-39
4-OCF3
N
N
C—CN
CH
CH
SO2




4-40
3-CO2Me
N
N
C—CF3
CH
CH
SO2




4-41
3-Me
CH
N
C—Cl
CH
CH
NH




4-42
4-tBu
CH
N
C—CN
CH
CH
NH




4-43
2-CH═CHMe
N
N
C—CF3
CH
CH
NH




4-44
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
NH




4-45
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
NH




4-46
2-CO2iPr-4-CF3
N
N
C—CN
CH
CH
NH




4-47
2-OnBu-4-CF3
N
N
C—CF3
CH
CH
Nme




4-48
2-OiBu-4-CF3
CH
N
C—Cl
CH
CH
Net




4-49
2-Oet-4-CF3
CH
N
C—CN
CH
CH
Nac




4-50
2-CO2iPr-4-CF3
N
N
C—CF3
CH
CH
Nac




4-51
2-OnPr-4-CF3
N
CH
C—CN
CH
CH
O
[124-125]



4-52
2-OCH2cPr-4-CF3
N
CH
C—CN
CH
CH
O
[129-131]



4-53
2-OCH2CHFMe-4-CF3
N
CH
C—CN
CH
CH
O
[105-109]



4-54
2-OCH2CH2Ome-4-CF3
N
CH
C—CN
CH
CH
O
nD24.7-











1.5697



4-55
2-CO2iPr-4-CF3
N
CH
C—CN
CH
CH
O
[133-135]



4-56
2-OCH2iPr-4-CF3
N
CH
C—CN
CH
CH
O
[139-141]



4-57
2-OCH2C(Me)═CH2-4-CF3
N
CH
C—CN
CH
CH
O
[90-93]



4-58
2-OCH2CH(Me)Ome-4-CF3
N
CH
C—CN
CH
CH
O
[114-118]



4-59
2-ON═C(Me)2-4-CF3
N
CH
C—CN
CH
CH
O
[125-128]



4-60
2-OnPr-4-OCF3
N
CH
C—CF3
CH
CH
NH
[89-90]



4-61
2-Ome-4-OCF3
N
CH
C—CF3
CH
CH
NH
[114-116]



4-62
2-OnPr-4-CF3
N
CH
C—CF3
CH
CH
NH
[96-97]



4-63
2-Me-3-CF3
N
CH
C—CF3
CH
CH
NH
[124-125]



4-64
2-OnPr-4-CF3
CH
CH
C—CF3
CH
CH
O
vis



4-65
2-OnPr-4-CF3
C—Cl
CH
C—CF3
CH
CH
O
[104-105]



4-66
2-OnPr-4-CF3
C—NO2
CH
C—CF3
CH
CH
O
vis



4-67
2-OnPr-4-CF3
C—F
CH
C—CF3
CH
CH
O
vis



4-68
2-OnPr-4-CF3
C—N(SO2Me)2
CH
C—CF3
CH
CH
O
amor



4-69
2-OnPr-4-CF3
CH
CH
C—Ome
CH
CH
O
[119-120]



4-70
2-OnPr-4-CF3
CH
C—F
C—CF3
CH
CH
O
vis



4-71
2-OnPr-4-CF3
CH
CH
C—OCF3
CH
CH
O
vis



4-72
2-OnPr-4-CF3
CH
CH
C—NO2
CH
CH
O
[114-117]



4-73
2-OnPr-4-CF3
CH
CH
C—NH2
CH
CH
O
vis



4-74
2-OnPr-4-CF3
CH
CH
C—NHS
CH
CH
O
[90-95]







O2CF3







4-75
2-OnPr-4-CF3
CH
CH
C—Br
CH
CH
O
vis



4-76
2-OnPr-4-CF3
CH
C—Cl
C—Cl
CH
CH
O
vis



4-77
2-OnPr-4-CF3
CH
CH
C-tBu
CH
CH
O
[139-141]



4-78
2-OnPr-4-CF3
CH
CH
C—Ph
CH
CH
O
[40-50]



4-79
2-OnPr-4-CF3
CH
C—Oet
C—CF3
CH
CH
O
vis



4-80
2-OnPr-4-CF3
CH
C-nPr
C—CF3
CH
CH
O
nD20.4-











1.4827



4-81
2-OnPr-4-CF3
CH
C—C═NOEt
C—CF3
CH
CH
O
[103-105]



4-82
2-OnPr-4-CF3
CH
C—CO2iPr
C—CF3
CH
CH
O
vis





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.













TABLES 10-11













 





















Physical constant


Compound






[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
X
point ° C.





5-1 
2-OnPr-4-CF3
N
N
C—CF3
S
O
[93-95]


5-2 
2-OCH2cPr-4-CF3
N
N
C—CF3
S
O
[110-112]


5-3 
2-CO2iPr-4-CF3
N
N
C—CF3
S
O
[112-114]


5-4 
2-ON═C(Me)2-4-CF3
N
N
C—CF3
S
O
[121-124]


5-5 
2-OiBu-4-CF3
N
N
C—CF3
S
O
[147-150]


5-6 
2-OCH2C(Me)═CH2-4-CF3
N
N
C—CF3
S
O
[121-124]


5-7 
2-OCH2CH(Me)OMe-4-CF3
N
N
C—CF3
S
O
 [98-102]


5-8 
2-OCH2CH(F)Me-4-CF3
N
N
C—CF3
S
O
[105-108]


5-9 
2-OnPr-4-CF3
C—CN
C—CF3
N
N—Me
O
[91-92]


5-10
2-OnPr-4-CF3
C—C(O)NH2
C—CF3
N
N—Me
O
[180-181]


5-11
4-CF3
CH
CH
CH
O
S



5-12
2-CF3-3-Cl
N
CH
Cme
O
S



5-13
4-CF3
CH
N
CH
O
S



5-14
4-CF3-2-OnPr
N
N
CH
O
S



5-15
3-CF3
N
N
CH
O
S



5-16
3-Me
O
CH
CH
NH
SO2



5-17
3-F
CH
CH
CH
NH
SO2



5-18
2-CN
CH
O
CH
NH
SO2



5-19
3-NO2
N
CH
C—CF3
NH
SO2



5-20
4-CHO
N
CH
CH
NH
SO2



5-21
4-Ome
CH
CH
CH
S
SO2



5-22
4-cPr
N
CH
CH
S
SO2



5-23
2-OcHex
N
CH
CH
S
NH



5-24
3-CH2CH2cPr
N
CH
CH
S
NH



5-25
4-OCH2cPr
N
CH
CH
S
NH



5-26
2-CHO
N
CH
CH
O
NH



5-27
3-OCH═CHMe
N
Cme
CH
O
Nme



5-28
2-CO2Et
CH
CH
CH
O
Nme





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.













TABLE 12













 





















Physical constant


Compound






[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
X
point ° C.





6-1
2-OnPr-4-CF3
N
NH
C—CF3
C
O
vis


6-2
2-OnPr-4-CF3
N
NMe
C—CF3
S
O



6-3
2-OCH2cPr-4-CF3
N
NH
C—CF3
S
O



6-4
2-CO2iPr-4-CF3
N
NH
C—CF3
S
S



6-5
2-ON═C(Me)2-4-CF3
N
NH
C—CF3
S
S



6-6
2-OiBu-4-CF3
N
Net
C—CF3
S
SO2



6-7
2-OCH2C(Me)═CH2-4-CF3
N
Nac
C—CF3
S
Nac



6-8
2-OCH2CH(Me)Ome-4-CF3
N
NH
C—CF3
S
NH



6-9
2-OCH2CH(F)Me-4-CF3
N
NH
C—CF3
S
NH



 6-10
2-OnPr-4-CF3
C—CN
CH—CF3
N
N—Me
O



 6-11
2-OnPr-4-CF3
C—C(O)NH2
Cme2
N
N—Me
O





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.













TABLES 13-14













 











Com-



Physical constant


pound



[ ]: Melting


No.
R2
X
R1
point ° C.





7-1 
5-CF3
O
2-OnPr-4-CF3
amor


7-2 
5-CF3
O
2-CHO-4-CF3
nD22.2-1.5330


7-3 
5-CF3
O
2-CH2OH-4-CF3
nD22.3-1.5194


7-4 
5-CF3
O
2-CH2OEt-4-CF3
nD22.3-1.5003


7-5 
3-Me
O
2-OnPr-4-CF3



7-6 
4-Ph
O
4-CF3



7-7 
3-OnPr
O
2-CF3-3-Cl



7-8 
3-OCH2cPr
O
4-CF3



7-9 
4-tBu
O
4-CF3-2-OnPr



7-10
4-OCH2CHFMe
O
3-CF3



7-11
—
S
3-Me



7-12
3-Br
S
3-F



7-13
4-CO2tBu
S
2-CN



7-14
3-CO2Et
S
3-NO2



7-15
2-OCF═CH2
S
4-CHO



7-16
5-OCH═CHMe
S
4-Ome



7-17
3-OCH2cPr
SO2
4-cPr



7-18
4-CH2CH2cPr
SO2
2-OcHex



7-19
3-OcPr
SO2
3-CH2CH2cPr



7-20
4-cPr
NH
4-OCH2cPr



7-21
5-OCF3
NH
2-OnPr-4-CF3



7-22
3,5-Me2
NH
4-CF3



7-23
6-Cl
NH
2-CF3-3-Cl



7-24
5-NO2
Nme
4-CF3



7-25
4-CHO
Nac
4-CF3-2-OnPr
















TABLES 15-16













 











Com-



Physical constant 


pound



[ ]: Melting 


No.
R2
X
R1
point ° C.





8-1 
5-CF3
O
5-CF3
nD22.7-1.5174


8-2 
5-CF3
O
3-Cl-5-CF3
nD23.0-1.5266


8-3 
3-Me
O
5-CF3



8-4 
3-F
O
4-cPr



8-5 
5-CN
S
3-OcPr



8-6 
5-NO2
S
3,5-Me2



8-7 
5-CHO
S
4-CF3



8-8 
4-OMe
S
5-CO2Et



8-9 
4-cPr
S
4-CH═CF2



8-10
5-OcHex
SO2
5-CH═Cme2



8-11
3-CH2CH2cPr
SO2
3-OCH2CH2cPr



8-12
4-OCH2cPr
SO2
4-CH2cPr



8-13
4-OCH═CH2
SO2
3-Oet-4-cPr



8-14
5-OCF3
SO2
4-CHO



8-15
4-OCH═CHCH2CF3
NH
5-NO2



8-16
4-CO2Et
NH
5-CF3



8-17
6-F
NH
4-cPr



8-18
6-CN
Nme
4-CO2Et



8-19
6-NO2
Nac
3-Me



8-20
6-OcPr
Nme
5-OCF3



8-21
3-Me
O
4-Ome



8-22
3-F
O
5-Cl



8-23
4-OCH═CF2
S
3-nBu
















TABLES 17-18













 















Physical constant


Compound



[ ]: Melting


No.
R2
X
R1
point ° C.





9-1 
6-CF3
O
2-OnPr-4-CF3
vis


9-2 
6-CF3
O
4-CF3
nD22.3-1.5245


9-3 
5-Me
O
2-CH2OEt-4-CF3



9-4 
6-CF3
O
2-Cl-4-CF3



9-5 
6-CF3
O
2-C(O)OiPr-4-CF3



9-6 
4-cPr
O
2,6-(NO2)2-4-CF3



9-7 
6-CF3
S
2-C(O)NHCH(Me)CH2OH-4-CF3



9-8 
6-OCH2CH2cPr
S
2-CH═NOEt-4-CF3



9-9 
5-OCH═Cme2
S
(E)-2-CH═NoiPr-4-CF3



9-10
6-CF3
S
2-CH═NO-propargyl-4-CF3



9-11
4-NO2
S
2-(5-Me-oxazoline-2-yl)-4-CF3



9-12
5-CHO
S
2-CH2Oet-4-CF3



9-13
5-Me
SO2
2-Ome-4-CF3



9-14
6-CF3
SO2
(Z)-2-CH═NoiPr-4-CF3



9-15
6-CF3
SO2
2-C(O)Oet-4-CF3



9-16
4-CN
SO2
2-C(O)OtBu-4-CF3



9-17
5-Br
NH
2-C(O)OiPr-4-CF3



9-18
4-OcPr
NH
6-Cl-2-C(O)OiPr-4-CF3



9-19
5-OtBu
NH
3-Br



9-20
5-OCH═CHMe
NH
4-Me



9-21
4-OCH═CHF
Nme
—



9-22
6-CO2Me
Nac
2-Cl
















TABLES 19-20













 























Physical constant


Compound







[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
Q5
X
point ° C.





10-1 
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[116-117]


10-2 
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
O
[112-113]


10-3 
2-OiBu-4-CF3
N
N
C—CF3
CH
CH
O
[148-149]


10-4 
2-CH2OEt-4-CF3
N
N
C—CF3
CH
CH
O
nD22.1-1.5088


10-5 
4-CF3
N
N
C—CF3
CH
CH
O
[130-131]


10-6 
2-OCH2CH(F)Me-4-CF3
N
CH
CH
N
C—Me
O



10-7 
2-OnPr-4-CF3
N
CH
CH
N
CH
O



10-8 
2-OnPr-4-CF3
N
CH
C—CF3
N
CH
S



10-9 
4-CF3
N
C—Br
CH
N
CH
S



10-10
2-CF3-3-Cl
N
CH
CH
CH
N
S



10-11
4-CF3
N
CH
C—CN
CH
CH
S



10-12
4-CF3-2-OnPr
N
C—CN
CH
CH
CH
S



10-13
3-CF3
N
CH
N
C—CF3
C—CF3
S



10-14
3-Me
CH
N
C—CN
CH
CH
S



10-15
3-F
N
CH
CH
CH
N
SO2



10-16
2-CN
C—Me
N
CH
CH
CH
SO2



10-17
3-NO2
N
C—F
CH
CH
N
NH



10-18
4-CHO
N
C—Cl
CH
CH
N
NH



10-19
4-Ome
N
CH
N
CH
CH
NH



10-20
4-cPr
CH
C—Me
N
C—Me
CH
NiPr



10-21
2-OcHex
CH
CH
N
CH
CH
Nme



10-22
3-CH2CH2cPr
CH
CH
N
CH
CH
Nme
















TABLE 21













 






















Physical










constant



Compound






[ ]: Melting



No.
R1
Q1
Q2
Q3
Q4
X
point ° C.
Remark





11-1
2-OnPr-4-CF3
N
N
C—CF3
S
O
vis



11-2
3-F
CH
CH
CH
S
O




11-3
2-CN
CH
CH
CH
O
O




11-4
3-NO2
N
CH
C—Me
S
S




11-5
4-CHO
N
C—F
CH
O
S




11-6
4-OMe
N
N
CH
NH
S




11-7
4-cPr
N
CH
CH
S
SO2




11-8
2-OcHex
N
CH
CH
Nme
SO2




11-9
3-CH2CH2cPr
N
N
CH
S
NH




 11-10
4-OCH2cPr
N
CH
CH
NH
NH




 11-11
2-CHO
CH
N
CH
NH
Nme
















TABLE 22













 















Physical






constant


Compound 



[ ]: Melting


No.
Q
X
R1
point ° C.





12-1 
5-CF3
O
2-NO2-4-CF3
[92-94]


12-2 
5-CF3
O
2-NH2-4-CF3
[120-122]


12-3 
5-CF3
O
2-NHAc-4-CF3
[145-147]


12-4 
5-CF3
O
2-OnPr-4-CF3
[104-106]


12-5 
5-CF3
O
2-C(O)OiPr-4-CF3
nD2l.8-1.5008 


12-6 
3-Cl
O
2-CH═NOEt-4-CF3



12-7 
4-CHO
O
(E)-2-CH═NOiPr-4-CF3



12-8 
6-NO2
S
2-CH═NO-propargyl-4-CF3



12-9 
4-OCH═CH2
S
2-(5-Me-oxazoline-2-yl)-4-CF3



12-10
5-OCF3
S
2-CH2Oet-4-CF3



12-11
4-OCH═CHCH2CF3
S
2-Ome-4-CF3



12-12
4-CO2Et
S
(Z)-2-CH═NoiPr-4-CF3



12-13
6-OCF3
SO2
2-C(O)Oet-4-CF3



12-14
6-CN
SO2
2-C(O)OtBu-4-CF3



12-15
6-NO2
SO2
2-C(O)OiPr-4-CF3



12-16
6-OcPr
NH
6-Cl-2-C(O)OiPr-4-CF3



12-17
3-Me
NH
3-Br



12-18
3-F
Net
4-cPr
















TABLE 23













 















Physical






constant


Compound



[ ]: Melting


No.
R2
X
R1
point ° C.





13-1 
5-CF3
O
5-CF3
[79-81]


13-2 
6-OnPr-5-CF3
O
5-CF3
[70-72]


13-3 
6-Cl-5-CF3
O
5-CF3
[100-102]


13-4 
4-NO2
O
4-cPr



13-5 
3-CO2iPr
O
3-OcPr



13-6 
4-OCH═CHF
S
3,5-Me2



13-7 
3-CH═CH2
S
4-CF3



13-8 
4-OCH2cPr
S
5-CO2Et



13-9 
5-CH2cPr
S
4-CH═CF2



13-10
3-OcPr
S
5-CH═CMe2



13-11
4-cPr
SO2
3-OCH2CH2cPr



13-12
4-OCHF2
NH
4-CH2cPr



13-13
3-Ome
NH
3-Oet-4-cPr



13-14
4-CN
NH
4-CHO



13-15
3-CHO
NH
5-NO2



13-16
5-NO2
Nme
5-CF3



13-17
4-F
Nac
4-cPr



13-18
3,5-Me2
Nac
4-CO2Et
















TABLE 24













 















Physical


Com-



constant


pound



[ ]: Melting


No.
R2
X
R1
point ° C.





14-1 
2-OiBu-6-CF3
O
5-CF3
nD22.5-






1.5074


14-2 
5-CF3-6-OnPr
O
5-CF3
[70-72]


14-3 
5-CHO
O
5-CF3



14-4 
4-OMe
O
4-cPr



14-5 
4-cPr
S
3-OcPr



14-6 
5-OcHex
S
3,5-Me2



14-7 
4-CH2CH2cPr
S
4-CF3



14-8 
4-OCH2cPr
S
5-CO2Et



14-9 
4-OCH═CH2
S
4-CH═CF2



14-10
5-OCF3
SO2
5-CH═Cme2



14-11
4-OCH═CHCH2CF3
SO
3-OCH2CH2cPr



14-12
4-CO2Et
SO
4-CH2cPr



14-13
6-F
NH
3-Oet-4-cPr



14-14
6-CN
NH
4-CHO



14-15
6-NO2
NH
4-Ome



14-16
6-OcPr
Nme
3-F



14-17
2-Me
Nac
4-CO2Me



14-18
2-F
Nac
5-CH2CH2cPr
















TABLE 25













 















Physical


Com-



constant


pound



[ ]: Melting


No.
R2
X
R1
point ° C.





15-1 
2-OCH2cPr-4-CF3
O
4-CF3
vis


15-2 
2-OCH2CH(F)Me-4-CF3
O
2-F



15-3 
2-OnPr-4-CF3
O
3,4-Me2



15-4 
2-OnPr-4-CF3
S
3-OMe



15-5 
4-CF3
S
3-CHO



15-6 
2-CF3-3-Cl
S
4-NO2



15-7 
4-CF3
SO
2-CO2Et



15-8 
4-CF3-2-OnPr
SO
3-CH═CHEt



15-9 
3-CF3
SO
4-OCH═CHMe



15-10
3-Me
SO2
3-OCF3



15-11
3-F
SO2
4-OCH═CF2



15-12
2-CN
NH
2-CF3-3-Cl



15-13
3-NO2
NH
4-CF3



15-14
2-CH═Cme2
NH
4-CF3-2-OnPr



15-15
3-OCH═CF2
Nac
3-CF3



15-16
4-CH2CH2CH2cPr
Nme
3-Me



15-17
2-OcPr-4-CF3
O
4-CF3
vis
















TABLES 26-29













 








 
























Physical











constant



Compound







[ ]: Melting



No.
R1
Q1
Q2
Q3
Q4
Q5
X
point ° C.
Remark





16-1 
2-OnPr-4-CF3
CH
N
C—CF3
CH
CH
O
[79-80]
cis


16-2 
2-OnPr-4-CF3
N
CH
C—CF3
N
CH
O
vis
cis


16-3 
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[100-103]
cis


16-4 
2-CO2iPr-4-CF3
N
N
C—CF3
CH
CH
O
vis
cis


16-5 
2-CH2OEt-4-CF3
N
N
C—CF3
CH
CH
O
 [99-102]
cis


16-6 
2-OCH2CH(Me)Ome-4-CF3
N
N
C—CF3
CH
CH
O
[103-105]
cis


16-7 
2-OnPr-4-CF3
N
N
C—Cl
CH
CH
O
[103-105]
cis


16-8 
2-OCH2cPr-4-CF3
N
N
C—CN
CH
CH
O
[106-108]
cis


16-9 
2-OCH2CH(Me)Ome-4-CF3
N
N
C—CN
CH
CH
O
[130-131]
cis


16-10
2-CH2OCH(Me)Ome-4-CF3
N
N
C—CF3
CH
CH
O
[132-135]
cis


16-11
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
O
[107-110]
cis


16-12
2-ON═C(Me)2-4-CF3
N
N
C—CF3
CH
CH
O
[121-124]
cis


16-13
2-ON═C(Me)Ome-4-CF3
N
N
C—CF3
CH
CH
O
[108-111]
cis


16-14
2-CO2iPr-4-CF3
N
N
C—CN
CH
CH
O
[153-155]
cis


16-15
2-ON═C(Me)2-4-CF3
N
N
C—CN
CH
CH
O
[132-134]
cis


16-16
2-OCH2C(Me)═CH2-4-CF3
N
N
C—CF3
CH
CH
O
[121-124]
cis


16-17
2-OiBu-4-CF3
N
N
C—CF3
CH
CH
O
[107-110]
cis


16-18
2-CH(OH)CH2iPr-4-CF3
N
N
C—CF3
CH
CH
O
[72-75]
cis


16-19
2-OCH2CH(F)Me-4-CF3
N
N
C—CF3
CH
CH
O
 [98-102]
cis


16-20
2-O(allyl)-4-CF3
N
N
C—CF3
CH
CH
O
[101-104]
cis


16-21
2-O(propargyl)-4-CF3
N
N
C—CF3
CH
CH
O
[107-111]
cis


16-22
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[206-209]
Sulfate











cis


16-23
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[220up]
Borate











cis


16-24
2-OCH2cPr-4-CF3
CH
N
C—CN
CH
CH
O
nD23.3-
cis










1.5840



16-25
2-OnPr-4-NO2
N
N
C—CF3
CH
CH
O
[128-132]
cis


16-26
2-OnPr-4-Cl
N
N
C—CF3
CH
CH
O
nD23.4-
cis










1.5447



16-27
4-CF3
N
N
C—CF3
CH
CH
O
[155-156]
cis


16-28
4-OCF3
N
N
C—CF3
CH
CH
O

cis


16-29
2-OCH2CH(Cl)Me-4-CF3
N
N
C—CF3
CH
CH
O
[101-105]
cis


16-30
2-OCH2cPr-4-CN
N
N
C—CF3
CH
CH
O
[136-138]
cis


16-31
2-NHnPr-4-CF3
N
N
C—CF3
CH
CH
O
[129-130]
cis


16-32
2-NHCH2cPr-4-CF3
N
N
C—CF3
CH
CH
O
[131-132]
cis


16-33
2-Br-4-CF3
N
N
C—CF3
CH
CH
O
[126-127]
cis


16-34
2-CF3-3-Cl
N
CH
CH
N
CH
S

cis


16-35
4-CF3
N
CH
CH
N
CH
S

cis


16-36
4-CF3-2-OnPr
N
CH
C—CF3
CH
N
S

cis


16-37
3-CF3
N
C—Br
CH
CH
N
SO

cis


16-38
3-Me
N
CH
N
CH
N
SO2

cis


16-39
3-F
N
CH
C—CN
CH
N
NH

cis


16-40
2-CN
N
C—CN
CH
CH
N
Nme

cis


16-41
4-CF3
N
N
C—CF3
CH
CH
O
[159-160]
trans


16-42
2-OniPr-4-CF3
N
N
C—CF3
CH
CH
O
[131-133]
trans


16-43
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
O
[112-114]
trans


16-44
2-CF3-3-Cl
N
N
C—CF3
CH
CH
S

trans


16-45
4-CF3
N
CH
CH
N
CH
S

trans


16-46
4-CF3-2-OnPr
N
CH
CH
N
CH
S

trans


16-47
3-CF3
N
CH
C—CF3
CH
N
SO

trans


16-48
3-Me
N
C—Br
CH
CH
N
SO

trans


16-49
3-F
N
CH
N
CH
N
SO

trans


16-50
2-CN
N
CH
C—CN
CH
N
SO2

trans


16-51
3-NO2
N
C—CN
CH
CH
N
SO2

trans


16-52
4-CHO
N
N
C—CF3
CH
CH
SO2

trans


16-53
4-Ome
N
N
C—CF3
CH
CH
SO2

trans


16-54
4-cPr
N
N
C—CF3
CH
CH
NH

trans


16-55
2-OcHex
N
N
C—CF3
CH
CH
NH

trans


16-56
3-CH2CH2cPr
N
CH
CH
N
CH
NH

trans


16-57
4-OCH2cPr
N
CH
CH
N
CH
Nme

trans


16-58
2-CHO
N
CH
CH
N
CH
Nme

trans


16-59
3-OCH ═CHMe
N
CH
CH
N
CH
Nac

trans


16-60
2-CO2Et
N
CH
CH
N
CH
Nac

trans


16-61
4-CF3
N
CH
C—CF3
CH
CH
NH
 [99-100]
cis


16-62
4-CF3
N
CH
C—CF3
CH
CH
Nac
[116-119]
cis


16-63
4-CF3
N
CH
C—CF3
CH
CH
Nme
[142-143]
cis


16-64
2-NO2-4-CF3
N
CH
C—CF3
CH
CH
NH
[140-143]
cis


16-65
2-NO2-4-CF3
N
CH
C—CF3
CH
CH
Nme
[124-127]
cis


16-66
2-NO2-4-CF3
N
CH
C—CF3
CH
CH
NnPr
amor
cis


16-67
2-NO2-4-CF3
N
CH
C—CF3
CH
CH
NnPr
amor
cis


16-68
2-NO2-4-CF3
N
CH
C—CF3
CH
CH
Net
[112-114]
cis


16-69
2-Me-4-OCF3
N
CH
C—CF3
CH
CH
NH
[89-90]
cis


16-70
2-Me-4-OCF3
N
CH
C—CF3
CH
CH
Nme
nD24.6-
cis










1.5115



16-71
2-Oet-4-tBu
N
CH
C—CF3
CH
CH
NH
vis
cis


16-72
2-Oet-4-tBu
N
CH
C—CF3
CH
CH
Nme
vis
cis


16-73
2-OnPr-4-CF3
N
CH
C—CF3
CH
CH
NH
[85-87]
cis


16-74
2-OnPr-4-CF3
N
CH
C—CF3
CH
CH
Nme
[101-103]
cis


16-75
2-nBu-4-CF3
N
CH
C—CF3
CH
CH
NH
[70-73]
cis


16-76
2,6-nBu2-4-CF3
N
CH
C—CF3
CH
CH
NH
nD22.0-
cis










1.5080



16-77
5-Cl-2-OnPr-4-CF3
N
CH
C—CF3
CH
CH
NH
vis
cis


16-78
2,6-Me2-4-OCF3
N
CH
C—CF3
CH
CH
NH
[70-73]
cis


16-79
2-OnPr-4-CF3
N
CH
C—CF3
CH
CH
NH
[103-104]
cis


16-80
2-OnPr-4-CF3
N
CH
C—CF3
CH
CH
NH
[107-109]
cis


16-81
2-OnPr-4-C(O)OtBu
N
CH
C—CF3
CH
CH
NH
[152-154]
cis


16-82
2-OnPr-4-CF3
N
CH
C—CN
CH
CH
O
[95-99]
cis


16-83
2-OCH2cPr-4-CF3
N
CH
C—CN
CH
CH
O
[87-89]
cis


16-84
2-OCH2Ome-4-CF3
N
CH
C—CN
CH
CH
O
[117-119]
cis


16-85
2-OCH2CH2Ome-4-CF3
N
CH
C—CN
CH
CH
O
[90-92]
cis


16-86
2-OCH2CH(Ome)Me-4-CF3
N
CH
C—CN
CH
CH
O
[78-81]
cis


16-87
2-CO2CHMe2-4-CF3
N
CH
C—CN
CH
CH
O
[142-145]
cis


16-88
2-CH2OCH(Me)Ome-4-CF3
N
CH
C—CN
CH
CH
O
[119-122]
cis


16-89
2-ON═Cme2-4-CF3
N
CH
C—CN
CH
CH
O
[120-122]
cis


16-90
2-ON═C(Ome)Me-4-CF3
N
CH
C—CN
CH
CH
O
[124-127]
cis


16-91
2-ON═C(NH2)Me-4-CF3
N
CH
C—CN
CH
CH
O
[142-145]
cis
















TABLE 30-31













 





















Physical









constant


Compound






[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
X
point ° C.





17-1 
2-OnPr-4-CF3
N
C—CF3
C—Br
S
O
vis


17-2 
2-OniPr-4-CF3
N
C—CF3
CH
S
O
vis


17-3 
2-OnPr-4-CF3
N
CH
C—CO2Me
S
O
[90-91]


17-4 
2-OnPr-4-CF3
N
CH
C—CH2OH
S
O
[135-137]


17-5 
2-OnPr-4-CF3
N
CH
C—CHO
S
O
[107-109]


17-6 
2-OnPr-4-CF3
N
CH
C—CF2H
5
O
vis


17-7 
2-OCH2cPr-4-CF3
N
N
C—CF3
S
O
vis


17-8 
2-CO2iPr-4-CF3
N
N
C—CF3
S
O
nD22.3-1.5038 


17-9 
2-OnPr-4-CF3
N
N
C—CF3
S
O
nD22.4-1.5148 


17-10
2-ON═C(Me)2-4-CF3
N
N
C—CF3
S
O
[113-115]


17-11
2-OnPr-4-CF3
CH
CH
CH
CH2
O
[140-142]


17-12
2-CF3-3-Cl
CH
CH
CH
NH
S



17-13
4-CF3
N
C—Cl
CH
NH
S



17-14
4-CF3-2-OnPr
N
CH
CH
NH
S



17-15
3-CF3
N
C—CN
CH
NH
S



17-16
3-Me
CH
CH
CH
O
SO



17-17
3-F
C—Cl
CH
C—Cl
O
SO



17-18
2-CN
N
CH
CH
O
SO



17-19
3-NO2
N
CH
CH
O
SO



17-20
4-CHO
CH
N
CH
O
SO



17-21
4-OMe
CH
N
CH
O
SO2



17-22
4-cPr
N
CH
CH
Nme
SO2



17-23
2-OcHex
N
CH
CH
Nme
NH



17-24
3-CH2CH2cPr
CH
N
CH
Nme
NH



17-25
4-OCH2cPr
CH
N
CH
Nme
NH



17-26
2-CHO
CH
N
CH
Nme
Nme
















TABLE 32













 





















Physical









constant


Compound






[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
X
point ° C.





18-1
2-OnPr-4-CF3
N
NH
C—CF3
CH
O
[140-142]


18-2
2-OnPr-4-CF3
N
CH2
C—Br
CH
O



18-3
2-OnPr-4-CF3
N
CMe2
CH
CH
O



18-4
2-OnPr-4-CF3
N
O
C—CO2Me
CH
S



18-5
2-OnPr-4-CF3
N
O
C—CH2OH
CH
S



18-6
2-OnPr-4-CF3
N
S
C—CHO
CH
SO2



18-7
2-OnPr-4-CF3
N
S
C—CF2H
C—Cl
NH



18-8
2-OCH2cPr-4-CF3
N
NH
C—CF3
Cme
NH



18-9
2-CO2iPr-4-CF3
N
Nme
C—CF3
C—CF3
NH



 18-10
2-OnPr-4-CF3
N
Nme
C—CF3
C—CF3
Nme



 18-11
2-ON═C(Me)2-4-CF3
N
Nme
C—CF3
C—CF3
O



 18-12
2-OnPr-4-CF3
CH
Nme
CH
CH
O
















TABLES 33-34













 























Physical










constant


Compound







[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
Q5
X
point ° C.





19-1 
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O
[125-127]


19-2 
2-OCH2cPr-4-CF3
N
N
C—CF3
CH
CH
O
[115-118]


19-3 
2-OEt-4-CF3
N
N
C—CF3
CH
CH
O
[141-143]


19-4 
2-OCH2OMe-4-CF3
N
N
C—CF3
CH
CH
O
[118-121]


19-5 
2-OiBu-4-CF3
N
N
C—CF3
CH
CH
O
[130-133]


19-6 
2-CO2iPr-4-CF3
N
N
C—CF3
CH
CH
O
amor


19-7 
2-CH2OEt-4-CF3
N
N
C—CF3
CH
CH
O
[144-146]


19-8 
2-OCH2CH(Me)OMe-
N
N
C—CF3
CH
CH
O
[114-115]



4-CF3









19-9 
2-OCH2cPr-4-CF3
CH
CH
CH
CH
CH
O
vis


19-10
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O



19-11
2-OnPr-4-CF3
N
N
C—CF3
CH
CH
O



19-12
4-CF3
N
CH
CH
N
C—Me
S



19-13
2-CF3-3-Cl
N
CH
CH
N
CH
S



19-14
4-CF3
N
CH
C—CF3
N
CH
S



19-15
4-CF3-2-OnPr
N
C—Br
CH
N
CH
S



19-16
3-CF3
N
CH
CH
CH
N
S



19-17
3-Me
N
CH
C—CN
CH
CH
SO



19-18
3-F
N
C—CN
CH
CH
CH
SO



19-19
2-CN
N
CH
N
CH
CH
SO



19-20
3-NO2
CH
N
C—CN
CH
CH
SO2



19-21
2-CH═CMe2
N
CH
CH
CH
N
SO2



19-22
3-OCH═CF2
C—Me
N
CH
CH
CH
SO2



19-23
4-CH2CH2CH2cPr
N
C—F
CH
CH
N
NH



19-24
2-OnPr-4-CF3
N
C—Cl
CH
CH
N
NH



19-25
2-OnPr-4-CF3
N
CH
N
CH
CH
NH



19-26
4-CHO
CH
C—Me
N
C—Me
CH
NMe



19-27
3-OCF3
N
N
C—CF3
CH
CH
NMe



19-28
2-CO2Et
N
N
CH
CH
CH
NAc
















TABLE 35













 





















Physical constant


Compound






[ ]: Melting


No.
R1
Q1
Q2
Q3
Q4
X
point ° C.





20-1 
2-OcPr-4-CF3
N
N
C—CF3
S
O
[116-119]


20-2 
2-CO2iPr-4-CF3
N
N
C—CF3
S
O
vis


20-3 
4-CF3
N
CH
C—Br
CH2
O



20-4 
4-CF3-2-OnPr
N
CMe
CH
CH2
O



20-5 
3-CF3
N
N
C—CO2Me
CH2
O



20-6 
3-Me
N
N
C—CH2OH
CH2
S



20-7 
3-F
N
CH
C—CHO
CH2
S



20-8 
2-CN
N
CH
C—CF2H
CH2
S



20-9 
3-NO2
N
N
C—CF3
Cme2
S



20-10
2-CH═Cme2
N
N
C—CF3
Cme2
SO



20-11
3-OCH═CF2
N
N
C—CF3
Cme2
SO



20-12
4-CH2CH2CH2cPr
N
N
C—CF3
CH2
SO2



20-13
2-OnPr-4-CF3
CH
N
CH
CH2
SO2



20-14
2-OnPr-4-CF3
N
CH
C—Br
CH2
SO2



20-15
4-CHO
N
Cme
CH
CH2
NH



20-16
3-OCF3
N
Cme
C—CO2Me
CH2
NH



20-17
4-cPr
CH
CH
N
NH
Nme

















TABLES 36-39

















 


















Physical constant



Compound




[ ]: Melting



No.
Cy1
X
Y
Cy1
point ° C.
cis/trans





21-1 




O
NH




vis
Cis


 


21-2 




O
NH




165-167
Trans


 


21-3 




O
NMe




vis
Cis


 


21-4 




O
NCO2Me




120-122
Cis


 


21-5 




O
S




nD22.2-1.5418 
Cis


 


21-6 




O
SO2




155-158
Cis


 


21-7 




O
O




156-157
Trans


 


21-8 




O
O




124-125
Cis


 


21-9 




O
O




125-126
Trans


 


21-10




O
O




vis
Cis


 


21-11




O
O




127-128
Trans


 


21-12




O
O




146-147
Cis


 


21-13




O
O




102-103
trans


 


21-14




O
S




125-128
Cis


 


21-15




O
S




52-55
Cis


 


21-16




O
S




136-138
Cis


 


21-17




O
SO2




200up
Cis


 


21{circumflex over ( )}18




O
O




93-95
Cis


 


21-19




O
SO2





Cis


 


21-20




O
SO2





Trans


 


21-21




S
NH





Cis


 


21-22




S
S





Cis


 


21-23




S
S





Trans


 


21-24




S
O





Trans


 


21-25




SO
Nme





Cis


 


21-26




SO2
NH





Trans


 


21-27




NH
SO2





Cis


 


21-28




NH
S





Trans


 


21-29




Nme
O





Cis
















TABLES 40-42













 
















Physical







constant



Compound



[ ]: Melting



No.
R2
X
R1
point ° C.
Remark





22-1 
5-CF3
O
2-OnPr-4-CF3
nD21.8-1.5022 



22-2 
5-CF3
O
2-CHO-4-CF3
vis



22-3 
5-CF3
O
2-CH2OH-4-CF3
vis



22-4 
5-CF3
O
2-CH2OCH(OMe)-4-CF3
90-92



22-5 
5-CF3
O
2-CH2Oet-4-CF3
nD22.4-1.4919 



22-6 
5-CF3
O
2-C(O)OiPr-4-CF3
vis
R3a = Et, trans


22-7 
5-CF3
O
2-C(O)OiiPr-4-CF3
vis
R3a = Et, cis


22-8 
5-CF3
O
2-C(O)OiPr-4-CF3
84-86



22-9 
5-CF3
O
2-OnPr-4-CF3
vis
R1a = Et, trans


22-10
5-CF3
O
2-OnPr-4-CF3
vis
R1a = Et, cis


22-11
5-CF3
O
4-CF3
nD22.3-1.5079 
R1a = Et, cis


22-12
5-CF3
O
4-CF3
nD22.2-1.5089 
R1a = Et, trans


22-13
5-CN
O
2-OnPr-4-CF3




22-14
5-CF3
O
2-CHO-4-CF3




22-15
3-Me
O
2-CH2OH-4-CF3




22-16
3-F
O
2-CH2OCH(Ome)Me-4-CF3

R1a = OH,







trans


22-17
5-CN
O
2-CH2Oet-4-CF3

R1a = F, cis


22-18
5-NO2
O
2-Cl-4-CF3




22-19
5-CHO
S
2-C(O)OiPr-4-CF3




22-20
4-Ome
S
2,6-(NO2)2-4-CF3




22-21
4-cPr
S
2-C(O)NHCH(Me)CH2OhiPr-4-CF3

R3a = Nme2,







trans


22-22
5-OcHex
S
2-CHNOEt-4-CF3

R1a = NO2, cis


22-23
3-CH2CH2cPr
S
2-CH═NoiPr-4-CF3




22-24
4-OCH2cPr
S
2-CH═NO-propargyl-4-CF3




22-25
4-OCH═CH2
S
2-(5-Me-oxazoline-2-yl)-4-CF3

R3a = CN,







trans


22-26
5-OCF3
S
2-CH2Oet-4-CF3




22-27
4-OCH═CHCH2CF3
S
2-Ome-4-CF3




22-28
4-CO2Et
SO
2-CHNoiPr-4-CF3




22-29
6-F
SO
2-C(O)Oet-4-CF3

R3a = CHO,







trans


22-30
6-CN
SO
2-C(O)OtBu-4-CF3

R1a = Ome,







cis


22-31
6-NO2
SO2
2-C(O)OiPr-4-CF3




22-32
6-OcPr
SO2
6-Cl-2-C(O)OiPr-4-CF3

R3a = OCF3,







trans


22-33
5-CN
SO2
2-CH═NOMe-4-CF3

R1a = CF3, cis


22-34
5-CF3
SO2
2-CH═NOMe-4-CF3




22-35
3-Me
SO2
2-C(O)OCH2cPr-4-CF3




22-36
3-F
SO2
2-C(O)OCH2CF3-4-CF3




22-37
5-CN
SO2
2-C(O)OiBu-4-CF3




22-38
5-NO2
SO2
2-C(O)OnPr-4-CF3




22-39
5-CHO
NH
2-CH(OH)CH2CH(Me)2-4-CF3

R1a = Sme, cis


22-40
4-Ome
NH
2-C(O)OCH(Me)CH═CH2-4-CF3




22-41
5-CF3
NH
2-C(O)OcPen-4-CF3

R3a = CO2Et,







trans


22-42
4-CF3-6-Cl
NH
2-C(O)ON═C(Me)2-4-CF3




22-43
5-CF3
NH
2-OCH2cPr-4-CF3




22-44
5-CF3-6-OnPr
NH
2-Oet-4-CF3




22-45
5-CF3
NH
2-C(O)OCH2CHF2-4-CF3




22-46
3-Me
NH
2-OnBu-4-CF3




22-47
3-F
NH
2-OnPr-4-CN




22-48
5-CN
NH
2-C(O)OCH2Ome-4-CF3

R1a =







C(S)Ome, cis


22-49
5-NO2
NH
2-C(O)OCH2tBu-4-CF3




22-50
5-CHO
NH
2-C(O)N(Me)2-4-CF3




22-51
4-Ome
NH
2-C(O)OCH(Me)CH(Me)2-4-CF3




22-52
4-cPr
NH
2-C(O)OCH(Et)2-4-CF3




22-53
5-OcHex
Nme
2-C(O)OtBu-4-CF3

R3a =







NHSO2Me,







trans


22-54
3-CH2CH2cPr
Nme
2-C(O)OiPr-4-CF3

R1a = Ph, cis


22-55
4-OCH2cPr
Nme
2-C(O)O(CH2)2Ome-4-CF3




22-56
6-Me
Nac
2-C(O)OCH(Me)CH2Ome-4-CF3




22-57
5-OcHex
Nac
2-C(O)OCH(CN)Me-4-CF3




22-58
3-CH2CH2cPr
NAC
2-C(O)OCH(Cl)Et-4-CF3




22-59
4-OCH═CH2
NCO2Me
2-C(O)SiPr-4-CF3




22-60
5-OCF3
NCO2Me
2-Obn-4-CF3

R3a =







N(SO2Me)2,







trans


22-61
4-OCH═CHCH2CF3
NCO2Me
2-OH-4-CF3

R1a = Et, cis


22-62
4-CO2Et
NCO2Me
2-OCH2CH(Me)Ome-4-CF3




22-63
4-CF3-5-Cl
NCO2Me
2-CH(OH)CH2CN-4-CF3




22-64
4-OCH═CHCH2CF3
NCO2Me
2-OnPr-4-CF3




22-65
—
NCO2Me
2-OCH2cPr-4-C3F7




22-66
6-Me
NCO2Me
4-Ph




22-67
5-OcHex
NCO2Me
2,3,4,5,6-F5





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.


Cis and trans represent positional relationship between X and (R1a, R2a, R3a, R4a, or R5).













TABLES 43-45













 
















Physical







constant



Compound



[ ]: Melting



No.
R2
X
R1
point ° C.
Remark





23-1 
5-CF3
O
5-CF3
84-86



23-2 
5-CF3-6-Cl
O
5-CF3
nD22.0-1.5150 



23-3 
5-CF3
O
5-CF3
nD22.0-1.5150 
R3a = Et, cis


23-4 
3-Cl-5-CF3
O
5-CF3
nD22.3-1.5149 
R3a = Et, trans


23-5 
5-CF3
O
5-CF3
nD22.4-1.5055 
R3a = Et, trans


23-6 
5-CF3
O
3-C(O)OiPr-4-CF3

R3a = Et, trans


23-7 
5-CF3
O
3-C(O)OiPr-4-CF3

R3a = Et, cis


23-8 
5-CF3
O
3-C(O)OiPr-4-CF3




23-9 
5-CF3
O
6-OnPr-4-CF3

R1a = Et, trans


23-10
5-CF3
O
6-OnPr-4-CF3

R1a = Et, cis


23-11
5-CF3
O
4-CF3

R1a = Et, cis


23-12
5-CF3
O
4-CF3

R1a = Et, trans


23-13
5-CN
O
5-OnPr-4-CF3




23-14
5-CF3
O
3-CHO-4-CF3




23-15
3-Me
O
3-CH2OH-4-CF3




23-16
3-F
O
3-CH2OCH(OMe)Me-4-CF3

R1a = OH, trans


23-17
5-CN
O
3-CH2Oet-4-CF3

R1a = F, cis


23-18
5-NO2
O
6-Cl-4-CF3




23-19
5-CHO
S
5-C(O)OiPr-4-CF3




23-20
4-Ome
S
5,6-(NO2)2-4-CF3




23-21
4-cPr
S
3-C(O)NHCH(Me)CH2OH-4-CF3

R3a = Nme2, trans


23-22
5-OcHex
S
3-CHNOEt-4-CF3

R1a = NO2, cis


23-23
3-CH2CH2cPr
S
3-CH═NoiPr-4-CF3




23-24
4-OCH2cPr
S
3-CH═NO-propargyl-4-CF3




23-25
4-OCH═CH2
S
3-(5-Me-oxazoline-2-yl)-4-CF3

R3a = CN, trans


23-26
5-OCF3
S
5-CH2Oet-4-CF3




23-27
4-OCH═CHCH2
S
5-Ome-4-CF3





CF3






23-28
4-CO2Et
SO
5-CH═NoiPr-4-CF3




23-29
6-F
SO
5-C(O)Oet-4-CF3

R3a = CHO, trans


23-30
6-CN
SO
3-C(O)OtBu-4-CF3

R1a = Ome, cis


23-31
6-NO2
SO2
3-C(O)OiPr-4-CF3




23-32
6-OcPr
SO2
6-Cl-2-C(O)OiPr-4-CF3

R3a = OCF3, trans


23-34
5-CN
SO2
3-CH═NOMe-4-CF3

R1a = CF3, cis


23-35
5-CF3
SO2
3-CH═NOMe-4-CF3




23-36
3-Me
SO2
3-C(O)OCH2cPr-4-CF3




23-37
3-F
SO2
5-C(O)OCH2CF3-4-CF3




23-37
5-CN
SO2
5-C(O)OiBu-4-CF3




23-38
5-NO2
SO2
5-C(O)OnPr-4-CF3




23-39
5-CHO
NH
5-CH(OH)CH2CH(Me)2-4-CF3

R1a = Sme, cis


23-40
4-Ome
NH
5-C(O)OCH(Me)CH═CH2-4-CF3




23-41
5-CF3
NH
5-C(O)OcPen-4-CF3

R3a = CO2Et, trans


23-42
4-CF3-6-Cl
NH
5-C(O)ON═C(Me)2-4-CF3




23-43
5-CF3
NH
5-OCH2cPr-4-CF3




23-44
5-CF3-6-OnPr
NH
5-Oet-4-CF3




23-45
5-CF3
NH
6-C(O)OCH2CHF2-4-CF3




23-46
3-Me
NH
6-OnBu-4-CF3




23-47
3-F
NH
6-OnPr-4-CN




23-48
5-CN
NH
6-C(O)OCH2Ome-4-CF3

R1a = C(S)Ome,







cis


23-49
5-NO2
NH
6-C(O)OCH2tBu-4-CF3




23-50
5-CHO
NH
6-C(O)N(Me)2-4-CF3




23-51
4-Ome
NH
6-C(O)OCH(Me)CH(Me)2-4-CF3




23-52
4-cPr
NH
3-C(O)OCH(Et)2-4-CF3




23-53
5-OcHex
Nme
3-C(O)Ome-4-CF3

R3a = NHSO2Me,







trans


23-54
3-CH2CH2cPr
Nme
3-C(O)OiPr-4-CF3

R1a = Ph, cis


23-55
4-OCH2cPr
Nme
3-C(O)O(CH2)2Ome-4-CF3




23-56
6-Me
Nac
3-C(O)OCH(Me)CH2Ome-4-CF3




23-57
5-OcHex
Nac
3-C(O)OCH(CN)Me-4-CF3




23-58
3-CH2CH2cPr
NAC
3-C(O)OCH(Cl)Et-4-CF3




23-59
4-OCH═CH2
NCO2Me
3-C(O)S(iPr)-4-CF3




23-60
5-OCF3
NCO2Me
3-Obn-4-CF3

R3a = N(SO2Me)2,







trans


23-61
4-OCH═CHCH2
NCO2Me
3-OH-4-CF3

R1a = Et, cis



CF3






23-62
4-CO2Et
NCO2Me
5-OCH2CH(Me)Ome-4-CF3




23-63
6-F
NCO2Me
5-C(O)OiPr-4-CF3




23-64
6-CN
NCO2Me
5-CH(OTMS)CH2CN-4-CF3




23-65
4-CF3-5-Cl
NCO2Me
5-CH(OH)CH2CN-4-CF3




23-66
4-OCH═CHCH2
NCO2Me
5-OnPr-4-CF3





CF3






23-67
—
NCO2Me
5-OCH2cPr-4-C3F7




23-68
6-Me
NCO2Me
4-Ph




23-69
5-OcHex
NCO2Me
3,4,5,6-F4





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.


Cis and trans represent positional relationship between X and (R1a, R2a, R3a, R4a, or R5).













TABLES 46-50













 
















Physical







constant



Compound



[ ]: Melting



No.
R2
X
R1
point ° C.
Remark





24-1 
4-CF3
O
2-NO2-4-CF3
vis



24-2 
4-CF3
O
2-NH2-4-CF3
80-82



24-3 
4-OCF3
O
2-NO2-4-CF3
nD23.0-1.5210 



24-4 
4-CF3
O
2-Br-4-CF3
nD23.0-1.5225 



24-5 
4-CF3
O
2-Cl-4-CF3
61-64



24-6 
4-CF3
O
2-F-4-CF3
56-58



24-7 
4-CF3
O
4-CF3
102-105



24-8 
2-Cl-4-CF3
O
4-CF3
vis



24-9 
2-Cl-4-CF3
O
2-F-4-CF3
nD22.5-1.5076 



24-10
4-CF3
O
4-CF3
nD22.4-1.5111 
R3a = Et, cis


24-11
4-CF3
O
4-CF3
nD22.5-1.5055 
R3a = Et, trans


24-12
5-CF3
O
4-CF3




24-13
4-CN
O
2-OnPr-4-CF3




24-14
5-CF3
O
3-CHO-4-CF3




24-15
4-Me
O
3-CH2OH-4-CF3




24-16
3-F
O
3-CH2OCH(OMe)Me-4-CF3

R1a = OH, trans


24-17
5-CN
O
2-CH2Oet-4-CF3

R1a = F, cis


24-18
5-NO2
O
6-Cl-4-CF3




24-19
5-CHO
S
5-C(O)OiPr-4-CF3




24-20
4-Ome
S
5,6-(NO2)2-4-CF3




24-21
4-cPr
S
3-C(O)NHCH(Me)CH2OH-4-CF3

R3a = Nme2, trans


24-22
5-OcHex
S
3-CH═NOEt-4-CF3

R1a = NO2, cis


24-23
3-CH2CH2cPr
S
3-CH═NoiPr-4-CF3




24-24
4-OCH2cPr
S
3-CH═NO-propargyl-4-CF3




24-25
4-OCH═CH2
S
3-(5-Me-oxazoline-2-yl)-4-CF3




24-26
5-OCF3
S
5-CH2Oet-4-CF3




24-27
4-OCH═CHCH2
S
2-Ome-4-CF3

R3a = CN, trans



CF3






24-28
4-CO2Et
SO
5-CH═NoiPr-4-CF3




24-29
6-F
SO
5-C(O)Oet-4-CF3

R3 a = CHO, trans


24-30
6-CN
SO
3-C(O)OtBu-4-CF3

R1a = Ome, cis


24-31
6-NO2
SO2
3-C(O)OiPr-4-CF3




24-32
6-OcPr
SO2
6-Cl-2-C(O)OiPr-4-CF3

R3a = OCF3, trans


24-33
5-CN
SO2
3-CH═NOMe-4-CF3

R1a = CF3, cis


24-34
5-CF3
SO2
3-CH═NOMe-4-CF3




24-35
3-Me
SO2
3-C(O)OCH2cPr-4-CF3




24-36
3-F
SO2
5-C(O)OCH2CF3-4-CF3




24-37
5-CN
SO2
5-C(O)OiBu-4-CF3




24-38
5-NO2
SO2
5-C(O)OnPr-4-CF3




24-39
5-CHO
NH
5-CH(OH)CH2CH(Me)2-4-CF3

R1a = Sme, cis


24-40
4-Ome
NH
5-C(O)OCH(Me)CH═CH2-4-CF3




24-41
5-CF3
NH
5-C(O)OcPen-4-CF3

R3a = CO2Et, trans


24-42
4-CF3-6-Cl
NH
5-C(O)ON═C(Me)2-4-CF3




24-43
5-CF3
NH
5-OCH2cPr-4-CF3




24-44
5-CF3-6-OnPr
NH
5-Oet-4-CF3




24-45
5-CF3
NH
6-C(O)OCH2CHF2-4-CF3




24-46
3-Me
NH
6-OnBu-4-CF3




24-47
3-F
NH
6-OnPr-4-CN




24-48
5-CN
NH
6-C(O)OCH2Ome-4-CF3

R1a =







C(S)Ome, cis


24-49
5-NO2
NH
6-C(O)OCH2tBu-4-CF3




24-50
5-CHO
NH
6-C(O)N(Me)2-4-CF3




24-51
4-Ome
NH
6-C(O)OCH(Me)CH(Me)2-4-CF3




24-52
4-cPr
NH
3-C(O)OCH(Et)2-4-CF3




24-53
5-OcHex
Nme
3-C(O)Ome-4-CF3

R3a =







NHSO2Me, trans


24-54
3-CH2CH2cPr
Nme
3-C(O)OiPr-4-CF3

R1a = Ph, cis


24-55
4-OCH2cPr
Nme
3-C(O)O(CH2)2Ome-4-CF3




24-56
6-Me
Nac
3-C(O)OCH(Me)CH2Ome-4-CF3




24-57
5-OcHex
Nac
3-C(O)OCH(CN)Me-4-CF3




24-58
3-CH2CH2cPr
NAC
3-C(O)OCH(Cl)Et-4-CF3




24-59
4-OCH═CH2
NCO2Me
3-C(O)SiPr-4-CF3




24-60
5-OCF3
NCO2Me
3-Obn-4-CF3

R3a = 







N(SO2Me)2, trans


24-61
4-OCH═CHCH2
NCO2Me
3-OH-4-CF3

R1a = Et, cis



CF3






24-62
4-CO2Et
NCO2Me
5-OCH2CH(Me)Ome-4-CF3




24-63
6-F
NCO2Me
5-C(O)OiPr-4-CF3




24-64
6-CN
NCO2Me
5-CH(OTMS)CH2CN-4-CF3




24-65
4-CF3-5-Cl
NCO2Me
5-CH(OH)CH2CN-4-CF3




24-66
4-OCH═CHCH2
NCO2Me
5-OnPr-4-CF3





CF3






24-67
—
NCO2Me
5-OCH2cPr-4-C3F7




24-68
6-Me
NCO2Me
4-Ph




24-69
5-OcHex
NCO2Me
3,4,5,6-F4





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.


Cis and trans represent positional relationship between X and (R1a, R2a, R3a, R4a, or R5).













TABLES 50-53













 






















Physical










constant



Compound






[ ]: Melting



No.
R1
X
Q1
Q2
Q3
Q4
point ° C.
Remark





25-1 
2-OnPr-4-CF3
O
N
N
C—CF3
S
nD22.2-1.4992
R3a = Et, cis


25-2 
2-OnPr-4-CF3
O
N
N
C—CF3
S
nD22.2-1.4998
R3a = Et, trans


25-3 
4-CF3
O
N
N
C—CF3
S
nD22.5-1.5041
R3a = Et, trans


25-4 
4-CF3
O
N
N
C—CF3
S
nD22.5-1.5034
R3a = Et, cis


25-5 
4-CF3
O
N
N
C—CF3
S
 [85-86]



25-6 
4-Cl
O
N
N
C—CF3
S
nD22.8-1.5354
R3a = Et, trans


25-7 
4-CF3
O
N
C—Cl
N
S
 [61-62]



25-8 
3-Cl
O
N
N
C—CF3
S
nD25.9-1.5374
R3a = Et, cis


25-9 
3-Cl
O
N
N
C—CF3
S
nD26.3-1.5368
R3a = Et, trans


25-10
4-Cl
O
N
N
C—CF3
S
nD26.3-1.5368
R3a = Et, cis


25-11
2-Cl
O
N
N
C—CF3
S
nD25.1-1.5414
R3a = Et, cis


25-12
2-Cl
O
N
N
C—CF3
S
nD25.5-1.5266
R3a = Et, trans


25-13
5-CN
O
N
CH
C—Br
CH2




25-14
5-NO2
O
N
CMe
CH
CH2




25-15
5-CHO
O
N
N
C—CO2Me
CH2




25-16
4-Ome
O
N
N
C—CH2OH
CH2




25-17
4-cPr
O
N
CH
C—CHO
CH2




25-18
5-OcHex
O
N
CH
C—CF2H
CH2

R1a = CHO, trans


25-19
3-CH2CH2cPr
O
N
N
C—CF3
Cme2

R1a = CN, trans


25-20
4-OCH2cPr
O
N
N
C—CF3
Cme2




25-21
4-OCH═CH2
S
N
N
C—CF3
Cme2




25-22
5-OCF3
S
N
N
C—CF3
CH2

R3a = CO2Me, trans


25-23
4-OCH═CHCH2CF3
S
CH
N
CH
CH2

R3a = Br, trans


25-24
4-CO2Et
S
N
CH
C—Br
CH2




25-25
6-F
S
N
Cme
CH
CH2




25-26
6-CN
S
N
Cme
C—CO2Me
CH2




25-27
6-NO2
S
CH
CH
N
NH




25-28
6-OcPr
S
N
CH
C—Br
CH2




25-29
5-CN
S
N
Cme
CH
CH2




25-30
5-CF3
S
N
N
C—CO2Me
CH2




25-31
3-Me
S
N
N
C—CH2OH
CH2




25-32
3-F
S
N
CH
C—CHO
CH2




25-33
5-CN
SO
N
CH
C—CF2H
CH2




25-34
5-NO2
SO
N
N
C—CF3
Cme2




25-35
5-CHO
SO
N
N
C—CF3
Cme2




25-36
4-Ome
SO
N
N
C—CF3
Cme2




25-37
5-CF3
SO
N
N
C—CF3
CH2




25-38
4-CF3-6-Cl
SO2
CH
N
CH
CH2




25-39
5-CF3
SO2
N
CH
C—Br
CH2




25-40
5-CF3-6-OnPr
SO2
N
Cme
CH
CH2

R1a = CF3, cis


25-41
5-CF3
SO2
N
Cme
C—CO2Me
CH2

R1a = Ome, cis


25-42
3-Me
SO2
CH
CH
N
NH

R3a = Nme2, trans


25-43
3-F
SO2
N
CH
C—Br
CH2




25-44
5-CN
SO2
N
Cme
CH
CH2




25-45
5-NO2
SO2
N
N
C—CO2Me
CH2




25-46
5-CHO
SO2
N
N
C—CH2OH
CH2




25-47
4-Ome
SO2
N
CH
C—CHO
CH2




25-48
4-cPr
SO2
N
CH
C—CF2H
CH2




25-49
5-OcHex
NH
N
N
C—CF3
Cme2




25-50
3-CH2CH2cPr
NH
N
N
C—CF3
Cme2

R3a = NO2, trans


25-51
4-OCH2cPr
NH
N
N
C—CF3
Cme2

R3a = Me, cis


25-52
6-Me
NH
N
N
C—CF3
CH2




25-53
5-OcHex
NH
CH
N
CH
CH2




25-54
3-CH2CH2cPr
NH
N
CH
C—Br
CH2




25-55
4-OCHCH2
NH
N
Cme
CH
CH2




25-56
5-OCF3
NH
N
Cme
C—CO2Me
CH2




25-57
4-OCH═CHCH2CF3
NH
CH
CH
N
NH




25-58
4-CO2Et
NH
N
CH
C—Br
CH2




25-59
6-F
NH
N
Cme
CH
CH2




25-60
6-CN
Nme
N
N
C—CO2Me
CH2

R3a = F, cis


25-61
4-CF3-5-Cl
Nme
N
N
C—CH2OH
CH2

R3a = Et, trans


25-62
4-OCH═CHCH2CF3
Nme
N
CH
C—CHO
CH2




25-63
—
Nme
N
CH
C—CF2H
CH2




25-64
6-Me
Nme
N
N
C—CF3
Cme2




25-65
5-OcHex
Nme
N
N
C—CF3
Cme2




25-66
5-CN
Nme
N
N
C—CF3
Cme2




25-67
5-NO2
Nac
N
N
C—CF3
CH2

R1a = SO2Me, trans


25-68
5-CHO
Nac
CH
N
CH
CH2

R1a = Et, cis


25-69
4-Ome
Nac
N
CH
C—Br
CH2




25-70
4-cPr
Nac
N
Cme
CH
CH2





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.


Cis and trans represent positional relationship between X and (R1a, R2a, R3a, R4a, or R5).













TABLES 54-57













 
























Physical











Constant



Compound







[ ]: Melting



No.
R1
X
Q1
Q2
Q3
Q4
Q5
point ° C.
Remark





26-1 
2-OEt-4-CF3
O
N
C—OiPr
N
C—CF3
CH
vis



26-2 
2-OnPr-4-CF3
O
N
N
C—CF3
CH
CH
 [106-109]



26-3 
2-OnPr-4-CF3
O
N
N
C—CF3
CH
CH
vis
R3a= Me, cis


26-4 
2-OnPr-4-CF3
O
N
N
C—CF3
CH
CH
vis
R3a= Me, trans


26-5 
2-OnPr-4-CF3
O
N
N
C—CF3
CH
CH
nD22.3-1.4992
R3a = Et, cis


26-6 
2-OnPr-4-CF3
O
N
N
C—CF3
CH
CH
amorphous
R3a = Et, trans


26-7 
—
O
N
N
C—Cl
CH
CH
vis
R3a = Et, cis


26-8 
4-CF3
O
N
N
C—Cl
CH
CH
nD26.3-1.5522
R3a = Et, trans


26-9 
4-CF3
O
N
N
C—CN
CH
CH
amorphous
R3a = Et, cis


26-10
4-CF3
O
N
N
C—CN
CH
CH
vis
R3a = Et, trans


26-11
4-CF3
O
N
N
C—CF3
CH
CH
 [108-109]



26-12
4-CF3
O
N
CH
N
C—CF3
CH
nD26.1-1.5093
R3a = Et, cis


26-13
4-CF3
O
N
CH
N
C—CF3
CH
nD26.2-1.5088
R3a = Et, trans


26-14
4-CF3
O
N
C—CF3
N
CH
CH
nD22.4-1.5071
R3= Et, trans


26-15
4-CF3
O
N
N
C—Cl
CH
CH
 [120-121]



26-16
4-CF3
O
N
N
C—CF3
CH
CH
nD25.5-1.5148
R3a = Et, cis


26-17
4-CF3
O
N
N
C—CF3
CH
CH
 [89-90]
R3a = Et, trans


26-18
4-CF3
O
H
N
C—Cl
CH
CH
nD25.2-1.5471
R3a = Et, cis


26-19
4-CF3
O
N
N
C—CF3
CH
CH
 [89-90]
R3a = Et, trans


26-20
2-OnPr-4-CF3
O
CH
CH
CH
CH
CH




26-21
4-CF3
O
N
N
C—CF3
CH
CH

R3a = F, trans


26-22
2-OnPr-4-CF3
O
N
N
C—CF3
CH
CH

R1a = Nme2, cis


26-23
4-CF3
O
N
CH
CH
N
C—Me




26-24
2-CH2OEt-4-CF3
O
N
CH
CH
N
CH




26-25
4-CF3
S
N
CH
C—CF3
N
CH




26-26
2,6-Me2
S
N
C—Br
CH
N
CH




26-27
4-OMe
S
N
CH
CH
CH
N




26-28
3-NO2
S
N
CH
C—CN
CH
CH




26-29
2-F
S
N
C—CN
CH
CH
CH

R3a = CN, cis


26-30
3-CHO
S
N
CH
N
CH
CH

R3a = NO2,











trans


26-31
3-OiPr
S
CH
N
C—CN
CH
CH




26-32
4-Me
S
N
CH
CH
CH
N




26-33
4-cPr
S
C—Me
N
CH
CH
CH




26-34
3-OcPr
SO
N
C—F
CH
CH
N

R1a = CHO, cis


26-35
4-CH2cPr
SO
N
C—Cl
CH
CH
N

R1a = OCF3,











trans


26-36
2-OCH2CH2cPr
SO
N
CH
N
CH
CH




26-38
3-OCH═CMe2
SO
CH
C—Me
N
C—Me
CH




26-39
4-OCF3
SO
N
N
C—CF3
CH
CH




26-40
4-OCF3
SO2
N
N
CH
CH
CH

R1a = OMe, cis


26-41
3-CO2Me
SO2
CH
CH
CH
CH
CH

R1a = CO2Et,











trans


26-42
3-Me
SO2
N
N
C—CF3
CH
CH




26-43
4-tBu
SO2
N
N
C—CF3
CH
CH




26-44
2-CH═CHMe
SO2
N
CH
CH
N
C—Me




26-45
2-OCH2cPr-4-CF3
SO2
N
CH
CH
N
CH




26-46
2-OCH2cPr-4-CF3
SO2
N
CH
C—CF3
N
CH




26-47
2-CO2iPr-4-CF3
SO2
N
C—Br
CH
N
CH




26-48
2-OnBu-4-CF3
SO2
N
CH
CH
CH
N




26-49
2-OiBu-4-CF3
NH
N
CH
C—CN
CH
CH




26-50
2-OEt-4-CF3
NH
N
C—CN
CH
CH
CH




26-51
2-CO2iPr-4-CF3
NH
N
CH
N
CH
CH




26-52
2-OnPr-4-CF3
NH
CH
N
C—CN
CH
CH




26-53
4-CF3
NH
N
CH
CH
CH
N

R3a = Et, trans


26-54
2-OnPr-4-CF3
NH
C—Me
N
CH
CH
CH

R1a = C(S)OMe,











cis


26-55
4-CF3
NH
N
C—F
CH
CH
N




26-56
2-CH2OEt-4-CF3
NH
N
C—Cl
CH
CH
N




26-57
4-CF3
NH
N
CH
N
CH
CH




26-58
2,6-Me2
NH
CH
C—Me
N
C—Me
CH




26-59
3-OCH═CMe2
NMe
CH
CH
CH
CH
CH

R1a = tBu, trans


26-60
4-OCF3
NMe
N
N
C—CF3
CH
CH

R3a = CH2cPr,











cis


26-61
4-OCF3
NMe
N
N
C—CF3
CH
CH




26-62
3-CO2Me
NMe
N
CH
CH
N
C—Me




26-63
4-tBu
Nme
N
CH
C—CF3
N
CH




26-64
2-CH═CHMe
NAc
N
C—Br
CH
N
CH




26-65
2-OCH2cPr-4-CF3
NAc
N
CH
CH
CH
N

R1a = Et, trans


26-66
3-OCH═CMe2
NAc
N
CH
C—CN
CH
CH

R3a = OMe, cis


26-67
4-OCF3
NAc
N
C—CN
CH
CH
CH




26-68
2-OCH2CH2OMe-4-CF3
O
N
CH
C—CN
CH
CH
 [57-60]





Note that R1b, R2b, R3a, R3b, R4a, R4b, and R5 represent hydrogen atom, respectively, unless otherwise indicated.


Cis and trans represent positional relationship between X and (R1a, R2a, R3a, R4a, or R5).






FORMULATION EXAMPLES
[Insecticides/Acaricides]
Although a few examples regarding compositions of the present invention are shown next, additives and proportions added are changeable over a wide range without being limited to these examples. Parts in Formulation Examples show parts by weight.
Formulation Example 1
Wettable Powder

















Compound of the present invention
40
parts



Diatomaceous earth
53
parts



Higher alcohol sulfate ester
4
parts



Alkylnaphthalenesulfonate salt
3
parts










The above components were mixed homogenously and ground finely to obtain a wettable powder with 40% of active ingredient.

Formulation Example 2
Emulsion

















Compound of the present invention
30
parts



Xylene
33
parts



Dimethylformamide
30
parts



Polyoxyethylene alkyl allyl ether
7
parts










The above components were mixed and dissolved to obtain an emulsion with 30% of active ingredient.

Formulation Example 3
Dusting Powder

















Compound of the present invention
10
parts



Talc
89
parts



Polyoxyethylene alkyl allyl ether
1
part










The above components were mixed homogenously and ground finely to obtain a dusting powder with 10% of active ingredient.

Formulation Example 4
Granules

















Compound of the present invention
5
parts



Clay
73
parts



Bentonite
20
parts



Sodium dioctylsulfosuccinate salt
1
part



Sodium phosphate
1
part










The above components were mixed and ground well and, after adding water thereto and kneading together, granulated and dried to obtain granules with 5% of active ingredient.

Formulation Example 5
Suspending Agent

















Compound of the present invention
10
parts



Sodium lignin sulfonate
4
parts



Sodium dodecylbenzenesulfonate
1
part



Xanthan gum
0.2
parts



Water
84.8
parts










The above components were mixed and subjected to wet-grinding until the grain size of 1 μm or less was achieved to obtain a suspending agent with 10% of active ingredient.

Next, usefulness of the compounds of the present invention as active ingredients of acaricides and insecticides are shown by Test Examples.
Test Example 1
Effectiveness Against Tetranychus urticae 
17 adult female Tetranychus urticae, which were resistant to organophosphorus pesticides, were inoculated on the first true leaf of a common bean, which was seeded in a pot with a diameter of 9 cm, where 7 to 10 days had passed after the germination. After the inoculation, the drug solution, which was prepared by following the method of the wettable powder shown in Example 1 of the drugs and by diluting with water to achieve the compound concentration of 125 ppm, was applied. The pot was placed in a temperature-controlled room where the temperature and humidity were set to 25° C. and 65% respectively, and the adulticidal rate was examined 3 days after the application. The test was repeated twice.
As a result, the compounds below showed the insecticidal rate of 100%. 1-1, 1-4 to 1-7, 1-10, 1-13, 1-17, 1-18, 1-21 to 1-29, 1-31 to 1-36, 1-39 to 1-47, 1-50, 1-51, 1-54, 2-3, 3-1, 4-5, 4-7, 4-9, 4-13, 4-16, 4-18 to 4-20, 4-53 to 4-55, 4-58 to 4-61, 4-64, 4-70, 4-71, 5-1 to 5-8, 10-1, 11-1, 13-2, 15-1, 15-7 16-1 to 16-26, 16-61, 16-65, 16-69, 16-73 to 16-75, 16-78, 16-82 to 16-91, 17-2, 17-3, 17-7 to 17-10, 19-1 to 19-3, 21-1, 21-3, 21-5, 21-6, 21-14 to 21-16, 22-1, 22-4, 22-5, 23-2, 25-1, 25-2, 26-3 to 26-6
Test Example 2
Effectiveness Against Panonychus citri 
10 adult female Panonychus citri were inoculated on the leaf of a mandarin orange, which was placed in a petri dish. After the inoculation, the drug solution, which was prepared by following the method of the emulsion shown in Example 2 of the drugs and by diluting with water to achieve the compound concentration of 125 ppm, was applied using a rotary spreading tower. The dish was placed in a temperature-controlled room where the temperature and humidity were set to 25° C. and 65% respectively, adults were removed 3 days after the application, and whether eggs laid during these 3 days could grow to become adults was examined on the 11th day.
As a result, the compounds below showed the insecticidal rate of 100%. 1-1, 1-5, 1-7, 1-13, 1-17, 1-24, 1-31, 1-32, 1-47, 1-50, 3-1, 4-5, 4-53, 4-54, 4-58 to 4-61, 4-64, 4-70, 4-71, 5-1, 5-2, 5-4, 5-8, 10-1, 12-4, 16-1 to 16-13, 16-15 to 16-20, 16-22, 16-23, 16-26, 16-61, 16-73, 16-83, 16-84, 16-89 to 16-91, 17-7, 17-9, 17-10, 19-1 to 19-3, 21-5, 21-6, 21-13, 22-1, 22-4, 23-2, 26-3, 26-5, 26-6
Test Example 3
Effectiveness Test Against Pseudaletia separata 
0.2 ml of a commercially available artificial diet (Insecta LFS manufactured by Nihon Nosan-Kogyo Co., Ltd) was put into a plastic test tube with a volume of 1.4 ml and was used as a test diet. The compound was adjusted to prepare 1% solution using dimethylsulfoxide containing 0.5% tween 20 and this solution was applied by adding dropwise onto the surface of the diet in an amount equivalent to 10 μg of the compound. 2 second-instar larvae of Pseudaletia separate were inoculated to each test tube and the tubes were sealed with plastic lids. The tubes were left at 25° C. and the insecticidal rate and amount of food ingested were examined after 5 days. The test was repeated twice.
In the present test, the compounds below were effective by showing the insecticidal rate of 100%, or the amount of food ingested was 10% or less compared to the solvent control group.
4-3, 4-4, 16-1, 16-2, 17-3, 17-7 to 17-9, 25-4
Test Example 4
Effectiveness Test Against Culex pipiens molestus 
10 larvae of Culex pipiens molestus, which were hatched 1 day before, and 0.225 ml of distilled water containing 0.5 mg of feed for aquarium fish (TetraMin® manufactured by Tetra Japan Co. Ltd) were put into a polystyrene test vessel with a volume of 0.3 ml. The compound was adjusted to prepare 1% solution using dimethylsulfoxide containing 0.5% tween 20 and further diluted to 0.01% with distilled water. This diluted drug solution was added to the test vessel with Culex pipiens molestus and was stirred (final compound concentration 0.001%). The vessels were left at 25° C. and the insecticidal rate was examined after 2 days. The test was repeated twice.
In the present test, the compound below was effective by showing the insecticidal rate of 90% or more.
4-3
While preferred embodiments of the invention have been described and illustrated above, it should be understood that these are exemplary of the invention and are not to be considered as limiting. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit or scope of the present invention. Accordingly, the invention is not to be considered as being limited by the foregoing description, and is only limited by the scope of the appended claims.
[Industrial Applicability]
According to the present invention, it is possible to provide agents for pest control with excellent bioactivities especially in terms of insecticidal/acaricidal activities and high safety and furthermore, it is possible to provide cyclic amine compounds with a novel structure, salts thereof, or N-oxides thereof.

## Claims

1. Agents for pest control comprising cyclic amine compounds represented by formula (1)




or salts thereof, or N-oxides thereof, as an active ingredient,
wherein Cy1 represents a group represented by formula (a) below,




wherein Y1 and Y2 represent a carbon atom and the symbol * represents the bonding positions, the group may be substituted by a halogen atom, a haloalkyl group, a haloalkoxy group, an alkoxy group, or an alkoxycarbonyl group;
X represents oxygen;
R, which does not form a ring, represents a hydroxyl group, a halogen atom, an amino group, a nitro group, or an alkyl group;
n is an integer from 0 to 9 and each R may be the same or different when n is 2 or more; and
Cy2 represents a heterocycle which may be substituted by a halogen atom, a haloalkyl group, an alkoxy group, or a cyano group, the heterocycle being furanyl, thiophenyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridinyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, piperidino, piperidyl, tetrahydrofuranyl, tetrahydropyranyl, pyrrolidinyl, piperidinyl, or piperazinyl, with the proviso that when Cy2 is pyridin-2-yl, Cy2 is substituted with at least one cyano group,
when Cy2 represents pyridazinyl, Cy2 is substituted with a haloalkyl group,
when Cy2 represents piperazinyl, Cy2 is substituted with a halogen atom, a haloalkyl group, an alkoxy group, or a cyano group,
when Cy2 represents thiazolyl, Cy2 is substituted with a haloalkyl group, or an alkoxy group, and
when Cy2 represents thiadiazolyl, Cy2 is substituted with a halogen atom, a haloalkyl group, or an alkoxy group.

2. Agents for pest control according to claim 1, wherein the agents for pest control are insecticides or acaricides.

3. Cyclic amine compounds represented by formula (2)




or salts thereof or N-oxides thereof,
wherein Cy3 represents any one of formulae (b) to (d) below,




wherein R6 represents haloalkyl or haloalkoxy,
R7 represents unsubstituted or substituted alkoxy, or unsubstituted or substituted alkoxycarbonyl;
R8 to R10 each independently represents halogen, haloalkyl, haloalkoxy, alkoxy (optionally substituted with G1),or alkoxycarbonyl;
G1 represents hydroxyl, halogen, amino, nitro, or an organic group;
k, and 1 each independently represents any one of an integer from 0 to 4 and each R8, and_each R9 may be the same or different when k, and_1, are 2 or more; m is any one of an integer from 0 to 5 and each R10 may be the same or different when m is 2 or more;
X represents oxygen;
R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, and R5 which do not form saturated rings together each independently represents a hydrogen, hydroxyl, halogen, unsubstituted or substituted amino, nitro, or an organic group;
Cy4 represents
pyridin-2-yl substituted with one or more cyano, pyridin-3-yl, pyridazin-3-yl, pyrazinyl, thiazol-2-yl, pyrimidin-2-yl, or 1,3,4-thiadiazol-2-yl, which are optionally substituted with G2 when Cy3 is a functional group represented by formula (c),
pyridin-2-yl substituted with one or more cyano, pyridin-3-yl, pyridazin-3-yl, pyrazinyl, thiazol-2-yl, pyrimidin-2-yl, or 1,3,4-thiadiazol-2-yl, which are optionally substituted with G2 when Cy3 is a functional group represented by formula (b) and
pyridin-2-yl substituted with one or more cyano, pyrazinyl, or 1,3,4-thiadiazol-2-yl which are optionally substituted with G2 when Cy3 is a functional group represented by formula (d);
G2 represents halogen, alkoxy (optionally substituted with G3), or haloalkyl;
and G3 represents hydroxyl, cyano, alkoxy, alkoxyalkoxy, or trialkylsilyloxy, and
when Cy4 represents thiazol-2-yl, Cy4 is substituted with a haloalkyl group or an alkoxy group, and
when Cy4 represents 1,3,4-thiadiazol-2-yl, Cy4 is substituted with a halogen atom, a haloalkyl group, or an alkoxy group.

4. Agents for pest control according to claim 1, wherein the heterocycle is selected from the group consisting of pyrrolyl, pyrazolyl, 1,3,4-thiadiazolyl, pyridinyl, pyridazinyl, pyrazinyl, and pyrimidinyl.