RU2473541C9 - Insecticidal aryl pyrrolidines - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention concerns novel aryl pyrrolidines of formula I:

, where X, which can be identical or different, denote halogen, halogen-C_1-6alkyl, NO₂, C_1-6alkyl, C_1-6alkoxy, CN, halogen-C_1-6alkoxy, C_1-6alkylthio, C_1-6alkylthionyl, C_1-6alkylsulphonyl, halogen- C_1-6alkylthio, halogen- C_1-6alkylthionyl, halogen- C_1-6alkylsulphonyl, OH, mercapto groups, NH₂, C_1-6alkylcarbonyl amino groups, halogen- C_1-6alkylcarbonyl-amino, C_1-6alkoxycarbonyl amino groups, halogen-C_1-6alkoxycarbonylamino; Y, which can be identical or different, denote halogen, halogen- C_1-6alkyl, NO₂, C_1-6alkyl, C_1-6alkoxy, CN, halogen- C_1-6alkoxy, C_1-6alkylthio, C_1-6alkylthionyl, C_1-6alkylsulphonyl, halogen- C_1-6alkylthio, halogen- C_1-6alkylthionyl, halogen- C_1-6alkylsulphonyl, hydroxyl groups, mercapto groups, NH₂, C_1-6alkylcarbonyl amino groups, halogen- C_1-6alkylcarbonyl amino, C_1-6alkoxycarbonyl amino groups, halogen- C_1-6alkoxycarbonyl amino; R denotes halogen- C_1-6alkyl; m equals 0, 1, 2, 3, 4, 5; n equals 1, 2, 3, 4; G denotes a group:

,

where R¹ and R² each independently denotes H, unsubstituted C_1-6alkyl, halogen- C_1-6alkyl, -CH₂R⁷;R³, R⁴ each independently denotes H; I equals 1, 2, 3; R⁵ denotes H; R⁶ denotes C_1-6alkylcarbonyl, a group: G6 - G8:

b where k³ equals 0; k⁴ equals 0; R⁷ denotes an unsubstituted 6-member heteroaryl with one N; A denotes C, N.

EFFECT: compounds exhibit insecticidal activity, which enables use thereof in insect and/or tick control method.

7 cl, 13 tbl, 8 ex

Description

The present invention relates to new arylpyrrolidines and their use as insecticides.

The application for international patent No. 2005/085216 describes that benzamide compounds with isoxazoline substituents can be used as agents for pest control.

The task of the inventors was to develop new compounds exhibiting higher activity and a wide spectrum of action in relation to such animal pests as insects and ticks. As a result, the inventors have found new arylpyrrolidines exhibiting very good or high activity and a wide spectrum of action; they are harmless to beneficial insects such as bees, and they act on insect pests, in particular insects that have become resistant to insecticides such as organophosphorus compounds and carbamate preparations.

Compounds according to the invention are represented by formula (I)

Where

X, which may be identical or different, halogen atoms mean halogenoalkyl groups, nitro, alkyl, alkoxy group, cyano group, halogenoalkoxyl, alkylthio, alkylsulfinyl, alkylsulfonyl, galogenalkiltiolnye, galogenalkilsulfinilnye, haloalkylsulfonyl, hydroxyl, mercapto, amino, alkylcarbonylamino, galogenalkilkarbonilaminogruppy, benzoylamino groups, alkoxycarbonylamino groups, haloalkoxycarbonylamino groups, alkylsulfonylamino groups and haloalkylsulfonyl and amino groups,

Y, which may be the same or different, means halogen atoms, haloalkyl groups, nitro groups, alkyl, alkoxy groups, cyano groups, haloalkoxy groups, alkylthiols, alkylsulfinyl, alkylsulfonyl, haloalkylthiols, halogenoalkylalkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkyl-alkylene benzoylamino groups, alkoxycarbonylamino groups, haloalkoxycarbonylamino groups, alkylsulfonylamino groups Do haloalkylsulfonyl-amino group,

R is an alkyl or haloalkyl group,

m takes the values 0, 1, 2, 3, 4 or 5,

n takes values 1, 2, 3 or 4,

G is selected from the group consisting of

Where

R ¹ and R ^2, independently of each other, each means a hydrogen atom, an unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl or alkylsulfonyl group, a haloalkylsulfonyl group or a CH ₂ -R ⁷ group, or together they mean an alkylene group with carbon atoms from two to six

R ³ and R ^4, independently of each other, each mean a hydrogen atom, a cyano group, an unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl group or together mean an alkylene group with two to six carbon atoms,

l takes the values 1, 2 or 3,

R ⁵ means a hydrogen atom, an alkyl, unsubstituted or substituted cycloalkyl group, a haloalkyl group, a cyano group, an alkenyl, alkynyl, alkylcarbonyl group or a CH ₂ -R ⁷ group,

R ⁶ represents formyl, cyano, alkylcarbonyl, alkylthiocarbonyl, haloalkylcarbonyl, haloalkyl, thiocarbonyl, alkylaminocarbonyl, alkylamino-thiocarbonyl, dialkylaminocarbonyl, dialkilaminotio-carbonyl, alkoksiaminokarbonilnuyu, alkoxyamino-thiocarbonyl group, alkoxycarbonyl, alkoxythiocarbonyl, tioalkoksikarbonilnuyu, tioalkoksitiokarbonilnuyu group, a group CO-R ⁷ , CS-R ⁷ , an alkylsulfonyl or haloalkylsulfonyl group, or alternatively

R ⁵ and R ^6, together with the nitrogen atom to which they are attached, form a cycle with a number of members from three to six, which includes at least one nitrogen atom and may include at least one other heteroatom selected from sulfur and oxygen, wherein the cycle may be substituted by a keto group or a thioketo group,

or from the group consisting of heterocycles from G1 to G9

Where

Z, which may be the same or different, mean halogen atoms, haloalkyl groups, nitro groups, alkyl, alkoxyl groups, cyano groups, haloalkoxyl, alkylsulfonyl, haloalkylsulfonyl, hydroxyl groups or mercapto groups,

k ¹ takes the values 0, 1, 2, 3 or 4,

k ² takes the values 0, 1, 2 or 3,

k ³ takes the values 0, 1 or 2,

k ⁴ takes the values 0 or 1,

R ⁷ means a phenyl or heterocyclic ring which may be substituted by at least one substituent selected from halogen atoms and alkyl groups with one to six carbon atoms, and

And means a carbon atom or nitrogen.

Among the compounds of formula (I) according to the invention, compounds of formula (Ia) are preferred

where X, Y, R, A, G, n and m have the above meaning.

Among the compounds of formula (I) or formula (Ia) according to the invention, compounds in which

X, which may be the same or different, mean halogen atoms, haloalkyl groups with one to six carbon atoms, nitro groups, alkyl groups with one to six carbon atoms, alkoxy groups with one to six carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to six, alkylthiol groups with the number of carbon atoms from one to six, alkylsulfinyl groups with the number of carbon atoms from one to six, alkylsulfonyl groups with the number of carbon atoms m one to six, haloalkylthiol groups with one to six carbon atoms, haloalkylsulfinyl groups with one to six carbon atoms, haloalkylsulfonyl groups with one to six carbon atoms, hydroxyl groups, mercapto groups, amino groups, alkylcarbonylamino groups with carbon atoms in the alkyl residue from one to six, a halogenated alkylcarbonylamino group with the number of carbon atoms in the halogenated alkyl residue from one to six, a benzoylamino group, alkoxycarbonylamino nN carbon atoms in the alkoxy radical of one to six, haloalkoxycarbonylamino carbon atoms in the haloalkoxy radical of one to six, alkylsulfonyl amino groups with a carbon number of one to six or haloalkyl-sulfonylamino carbon atoms from one to six,

Y, which may be the same or different, mean halogen atoms, haloalkyl groups with one to six carbon atoms, nitro groups, alkyl groups with one to six carbon atoms, alkoxy groups with one to six carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to six, alkylthiol groups with the number of carbon atoms from one to six, alkylsulfinyl groups with the number of carbon atoms from one to six, alkylsulfonyl groups with the number of carbon atoms m one to six, haloalkylthiol groups with one to six carbon atoms, haloalkylsulfinyl groups with one to six carbon atoms, haloalkylsulfonyl groups with one to six carbon atoms, hydroxyl groups, mercapto groups, amino groups, alkylcarbonylamino groups with carbon atoms in the alkyl residue from one to six, a halogenated alkylcarbonylamino group with the number of carbon atoms in the halogenated alkyl residue from one to six, a benzoylamino group, alkoxycarbonylamino nN carbon atoms in the alkoxy radical of one to six, haloalkoxycarbonylamino carbon atoms in the haloalkoxy radical of one to six, alkylsulfonyl amino groups with a carbon number of one to six or haloalkyl-sulfonylamino carbon atoms from one to six,

R is an alkyl group with one to six carbon atoms or a haloalkyl group with one to six carbon atoms,

m takes the values 0, 1, 2, 3, 4 or 5,

n takes values 0, 1, 2 or 4,

G is selected from the group consisting of

or from the group consisting of heterocycles from G1 to G9

Where

R ¹ and R ^2, independently of each other, each means a hydrogen atom, an unsubstituted or substituted alkyl group with the number of carbon atoms from one to six, an alkenyl group with the number of carbon atoms from two to six, an alkynyl group with the number of carbon atoms from two to six, a cycloalkyl group having a carbon number of three to seven, an alkylsulfonyl group having a carbon number of one to six, a haloalkylsulfonyl group having a carbon number of one to six, or a group CH ₂ -R ⁷ or together represent an alkylene GRU n, with the number of carbon atoms from two to six,

R ³ and R ^4, independently of each other, each means a hydrogen atom, a cyano group, an unsubstituted or substituted alkyl group with the number of carbon atoms from one to six, an alkenyl group with the number of carbon atoms from two to six, an alkynyl group with the number of carbon atoms from two to six, a cycloalkyl group with a carbon number of three to seven, or an alkoxycarbonyl group with a carbon number of one to six alkoxyl radicals or together mean an alkylene group with a carbon number of two to six,

l takes the values 1, 2 or 3,

R ⁵ means a hydrogen atom, an alkyl group with one to six carbon atoms, an unsubstituted or substituted cycloalkyl group with three to seven carbon atoms, a haloalkyl group with one to six carbon atoms, a cyano group, an alkenyl group with carbon atoms from two to six, an alkynyl group with two to six carbon atoms, an alkylcarbonyl group with one to six carbon atoms or a CH ₂ -R ⁷ group,

R ⁶ means a formyl group, a cyano group, an alkylcarbonyl group with the number of carbon atoms in the alkyl residue from one to six, an alkylthiocarbonyl group with the number of carbon atoms in the alkyl residue from one to six, a haloalkylcarbonyl group with the number of carbon atoms in the halogen radical of one to six, a halogenated alkylthiocarbonyl group with one to six carbon atoms in the halogenated alkyl radical; an alkylaminocarbonyl group with one to six carbon atoms in the alkyl radical; alkyl a minothiocarbonyl group with one to six carbon atoms in the alkyl residue, a dialkylaminocarbonyl group with two to eight alkyl atoms, a dialkylamino-thiocarbonyl group with two to eight carbon atoms, an alkoxyaminocarbonyl group with carbon atoms in the alkoxyl radical of one to six, an alkoxyamino-thiocarbonyl group with the number of carbon atoms in the alkoxyl radical of one to six, the alkoxycarbonyl group with the number of atoms one to six alkoxy radicals, one to six alkoxythiocarbonyl group with one to six carbon alkoxy radicals, one to six alkoxy carbonyl group with one to six carbon alkoxy radicals, thioalkoxythiocarbonyl carbon group with six carbon atoms , a CO-R ⁷ group, CS-R ⁷ , an alkylsulfonyl group with one to six carbon atoms or a haloalkylsulfonyl group with one to six carbon atoms, or

R ⁵ and R ^6, together with the nitrogen atom to which they are attached, form a cycle with a number of members from three to six, which includes at least one nitrogen atom and may include at least one other heteroatom selected from sulfur and oxygen, wherein the cycle may be substituted by a keto group or a thioketo group,

Z, which may be the same or different, mean halogen atoms, haloalkyl groups with one to six carbon atoms, nitro groups, alkyl groups with one to six carbon atoms, alkoxy groups with one to six carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to six, alkylsulfonyl groups with the number of carbon atoms from one to six, halogenated alkylsulfonyl groups with the number of carbon atoms from one to six, hydroxyl groups or mercapto groups .

k ¹ takes the values 0, 1, 2, 3 or 4,

k ² takes the values 0, 1, 2 or 3,

k ³ takes the values 0 or 1,

k ⁴ takes the values 0 or 1,

R ⁷ means a phenyl or heterocyclic ring which may be substituted by at least one substituent selected from fluorine, chlorine, bromine, iodine, and alkyl groups with one to six carbon atoms, and

And means a carbon atom or nitrogen.

Other compounds of formula (I) or formula (Ia) which are preferred according to the invention are those in which

X, which may be the same or different, mean halogen atoms, haloalkyl groups with one to six carbon atoms, nitro groups, alkyl groups with one to six carbon atoms, alkoxy groups with one to six carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to six, alkylthiol groups with the number of carbon atoms from one to six, alkylsulfinyl groups with the number of carbon atoms from one to six, alkylsulfonyl groups with the number of carbon atoms m one to six, haloalkylthiol groups with one to six carbon atoms, haloalkylsulfinyl groups with one to six carbon atoms, haloalkylsulfonyl groups with one to six carbon atoms, hydroxyl groups, mercapto groups, amino groups, alkylcarbonylamino groups with the number of atoms carbon in the alkyl residue from one to six, halogenated alkylcarbonylamino group with the number of carbon atoms in the halogenated alkyl residue from one to six, benzoylamino group, alkoxycarbonyl amino groups with the number of carbon atoms in the alkoxy radical from one to six, a halogenoalkoxycarbonylamino group with the number of carbon atoms in the halogenoalkoxy radical of one to six, an alkylsulfonylamino group with the number of carbon atoms from one to six or a halogenoalkylsulfonylamino group with the number of carbon atoms from one to six,

Y, which may be the same or different, mean halogen atoms, haloalkyl groups with one to six carbon atoms, nitro groups, alkyl groups with one to six carbon atoms, alkoxy groups with one to six carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to six, alkylthiol groups with the number of carbon atoms from one to six, alkylsulfinyl groups with the number of carbon atoms from one to six, alkylsulfonyl groups with the number of carbon atoms m one to six, haloalkylthiol groups with one to six carbon atoms, haloalkylsulfinyl groups with one to six carbon atoms, haloalkylsulfonyl groups with one to six carbon atoms, hydroxyl groups, mercapto groups, amino groups, alkylcarbonylamino groups with carbon atoms in the alkyl residue from one to six, a halogenated alkylcarbonylamino group with the number of carbon atoms in the halogenated alkyl residue from one to six, a benzoylamino group, alkoxycarbonylamino nN carbon atoms in the alkoxy radical of one to six, haloalkoxycarbonylamino carbon atoms in the haloalkoxy radical of one to six, alkylsulfonyl amino groups with a carbon number of one to six or haloalkyl-sulfonylamino carbon atoms from one to six,

R is an alkyl group with one to six carbon atoms or a haloalkyl group with one to six carbon atoms,

m takes values 0, 1, 2 or 3,

n takes values 0, 1, 2 or 3,

G is selected from the group consisting of

or from the group consisting of heterocycles from G1 to G9

Where

R ¹ and R ^2, independently of each other, each means a hydrogen atom, an alkyl group with one to six carbon atoms that can be substituted, an alkenyl group with two to six carbon atoms that can be substituted, an alkynyl group with carbon atoms from two to six, which may be substituted, a cycloalkyl group with the number of carbon atoms from three to seven, which may be substituted, an alkylsulfonyl group with the number of carbon atoms from one to six, a haloalkylsulfonyl group with the number of atoms s carbon by one to six, or a group CH ₂ -R ⁷ or together represent an alkylene group with carbon atoms from three to five,

R ³ and R ^4, independently of each other, each means a hydrogen atom, a cyano group, an alkyl group with one to six carbon atoms that can be substituted, an alkenyl group with two to six carbon atoms that can be substituted, an alkynyl group with two to six carbon atoms that can be substituted, a cycloalkyl group with three to seven carbon atoms that can be substituted, or an alkoxycarbonyl group with one to six carbon atoms in the alkoxyl radical, or together mean an alkylene group with three to five carbon atoms,

l takes the values 1 or 2,

R ⁵ means a hydrogen atom, an alkyl group with one to six carbon atoms, a cycloalkyl group with three to seven carbon atoms that may be substituted, a haloalkyl group with one to six carbon atoms, a cyano group, an alkenyl group with the number carbon atoms from two to six, an alkynyl group with the number of carbon atoms from two to six, an alkylcarbonyl group with the number of carbon atoms in the alkyl residue from one to six or a CH ₂ -R ⁷ group,

R ⁶ means a formyl group, a cyano group, an alkylcarbonyl group with the number of carbon atoms in the alkyl residue from one to six, an alkylthiocarbonyl group with the number of carbon atoms in the alkyl residue from one to six, a haloalkylcarbonyl group with the number of carbon atoms in the halogen radical of one to six, a halogenated alkylthiocarbonyl group with one to six carbon atoms in the halogenated alkyl radical; an alkylaminocarbonyl group with one to six carbon atoms in the alkyl radical; alkyl a minothiocarbonyl group with one to six carbon atoms in the alkyl residue, a dialkylaminocarbonyl group with two to eight alkyl atoms, a dialkylamino-thiocarbonyl group with two to eight carbon atoms, an alkoxyaminocarbonyl group with carbon atoms in the alkoxyl radical of one to six, an alkoxyamino-thiocarbonyl group with the number of carbon atoms in the alkoxyl radical of one to six, the alkoxycarbonyl group with the number of atoms one to six alkoxy radicals, one to six alkoxythiocarbonyl group with one to six carbon alkoxy radicals, one to six alkoxy carbonyl group with one to six carbon alkoxy radicals, thioalkoxythiocarbonyl carbon group with six carbon atoms , a group CO-R ⁷ , CS-R ⁷ , an alkylsulfonyl group with one to six carbon atoms or a haloalkylsulfonyl group with one to six carbon atoms, or alternatively in the case of

R ⁵ and R ^6, together with the nitrogen atom to which they are connected, form a cycle with a number of members from three to six, which includes at least one nitrogen atom and may include at least another heteroatom selected from sulfur and oxygen, with this cycle can be replaced by a keto group or thioketo group,

Z, which may be the same or different, mean halogen atoms, haloalkyl groups with one to six carbon atoms, nitro groups, alkyl groups with one to six carbon atoms, alkoxy groups with one to six carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to six, alkylsulfonyl groups with the number of carbon atoms from one to six, halogenated alkylsulfonyl groups with the number of carbon atoms from one to six, hydroxyl groups or mercapto groups .

k ¹ takes the values 0, 1, 2 or 3,

k ² takes the values 0, 1 or 2,

k ³ takes the values 0 or 1,

k ⁴ takes the values 0 or 1,

R ⁷ means a phenyl or heterocyclic ring which may be substituted by at least one substituent selected from fluorine, chlorine, bromine and alkyl groups with one to six carbon atoms, and

And means a carbon atom or nitrogen.

Among these compounds of formula (I) or formula (Ia), compounds in which

X, which may be the same or different, mean halogen atoms, haloalkyl groups with one to four carbon atoms, nitro groups, alkyl groups with one to four carbon atoms, alkoxy groups with one to four carbon atoms, cyano groups, haloalkoxy groups with the number of carbon atoms from one to four, alkylthiol groups with the number of carbon atoms from one to four, alkylsulfinyl groups with the number of carbon atoms from one to four, alkylsulfonyl groups with the number of atom carbon atoms from one to four, haloalkylthiol groups with one to four carbon atoms, haloalkylsulfinyl groups with one to four carbon atoms, haloalkylsulfonyl groups with one to four carbon atoms, hydroxyl groups, mercapto groups, amino groups, alkylcarbonylamino groups with the number carbon atoms in the alkyl residue from one to four, halogenated alkylcarbonylamino group with the number of carbon atoms in the halogenated alkyl residue from one to four, benzoylamino group, alkoxycarbonylamino groups with one to four carbon atoms in the alkoxy radical; one to four halogen alkoxycarbonylamino groups with one to four carbon alkoxycarbonyl radicals; one to four carbon sulfonylamino radicals or one to four carbon atoms;

Y, which may be the same or different, means halogen atoms, haloalkyl groups with the number of carbon atoms from one to four, nitro groups, alkyl groups with the number of carbon atoms from one to four, alkoxy groups with the number of carbon atoms from one to four, cyano group, haloalkoxy group with the number of carbon atoms from one to four, alkylthiol groups with the number of carbon atoms from one to four, alkylsulfinyl groups with the number of carbon atoms from one to four, alkylsulfonyl groups with the number of atom carbon atoms from one to four, haloalkylthiol groups with one to four carbon atoms, haloalkylsulfinyl groups with one to four carbon atoms, haloalkylsulfonyl groups with one to four carbon atoms, hydroxyl groups, mercapto groups, amino groups, alkylcarbonylamino groups with the number carbon atoms in the alkyl residue from one to four, halogenated alkylcarbonylamino group with the number of carbon atoms in the halogenated alkyl residue from one to four, benzoylamino group, alkoxycarbonylamino groups with one to four carbon atoms in the alkoxy radical; one to four haloalkoxycarbonylamino amino groups with one to four carbon atoms in the haloalkylamino alkyl radical; one to four carbon atoms or one to four haloalkyl amino groups with one to four carbon atoms

R is an alkyl group with one to four carbon atoms or a haloalkyl group with one to four carbon atoms,

m takes values 0, 1, 2 or 3,

n takes values 0, 1, 2 or 3,

G is selected from the group consisting of

or from the group consisting of heterocycles from G1 to G9

Where

R ¹ and R ^2, independently of each other, each means a hydrogen atom, an alkyl group with one to four carbon atoms that can be substituted, an alkenyl group with two to four carbon atoms that can be substituted, an alkynyl group with carbon atoms from two to four, which may be substituted, a cycloalkyl group with the number of carbon atoms from three to six, which may be substituted, an alkylsulfonyl group with the number of carbon atoms from one to four, halogenated alkylsulfonyl group with the number of carbon atoms from one to four or a group CH ₂ -R ⁷ or together mean an alkylene group with the number of carbon atoms from three to five,

R ³ and R ^4, independently of each other, each means a hydrogen atom, a cyano group, an alkyl group with one to four carbon atoms that can be substituted, an alkenyl group with two to four carbon atoms that can be substituted, an alkynyl group with two to four carbon atoms that can be substituted, a cycloalkyl group with three to six carbon atoms that can be substituted, or an alkoxycarbonyl group with one to four carbon atoms in the alkoxyl radical ex or together denote an alkylene group with carbon atoms from three to five,

l takes the values 1 or 2,

R ⁵ means a hydrogen atom, an alkyl group with one to four carbon atoms, a cycloalkyl group with three to six carbon atoms that may be substituted, a haloalkyl group with one to four carbon atoms, a cyano group, an alkenyl group with the number carbon atoms from two to four, alkynyl group with the number of carbon atoms from two to four, an alkylcarbonyl group with the number of carbon atoms in the alkyl residue from one to four or a CH ₂ -R ⁷ group,

R ⁶ means a formyl group, a cyano group, an alkylcarbonyl group with one to four carbon atoms in the alkyl radical, one to four alkylthiocarbonyl groups with one to four carbon atoms in the alkyl radical, one to four halogenated alkylcarbonyl groups, a haloalkylthiocarbonyl group with one to four carbon atoms in the halogenated alkyl radical; an alkylaminocarbonyl group with one to four carbon atoms in the alkyl radical pech, an alkylaminothiocarbonyl group with one to four carbon atoms in the alkyl radical, a dialkylaminocarbonyl group with two to eight carbon radicals, a dialkylamino-thiocarbonyl group with two to eight carbon atoms in the alkyl radical, alkoxyaminocarbonyl group with the number carbon atoms in the alkoxyl radical of one to four, alkoxyamino-thiocarbonyl group with the number of carbon atoms in the alkoxyl radical of one to four, alkoxycarbonyl group with the number of carbon atoms in the alkoxyl radical from one to four, an alkoxythiocarbonyl group with the number of carbon atoms in the alkoxyl radical of one to four, a thioalkoxycarbonyl group with the number of carbon atoms in the thioalkoxy radical from one to four, the thioalkoxythiocarbonyl group with the number of carbon atoms in the thioalkoxy radical one to four, the group CO-R ^7, CS-R ^7, an alkylsulfonyl group having a carbon number from one to four or haloalkylsulfonyl group with carbon atoms from one of up to four, or alternatively,

R ⁵ and R ^6, together with the nitrogen atom to which they are attached, form a cycle with a number of members from three to six, which includes at least one nitrogen atom and may include at least one other heteroatom selected from sulfur and oxygen, wherein the cycle may be substituted by a keto group or a thioketo group,

Z, which may be the same or different, mean halogen atoms, haloalkyl groups with one to four carbon atoms, nitro groups, alkyl groups with one to four carbon atoms, alkoxy groups with one to four carbon atoms, cyano groups, haloalkoxy groups with one to four carbon atoms, alkylsulfonyl groups with one to four carbon atoms, haloalkylsulfonyl groups with one to four carbon atoms, hydroxyl groups or m rkaptogruppy,

k ¹ takes the values 0, 1, 2 or 3,

k ² takes the values 0, 1 or 2,

k ³ takes the values 0 or 1,

k ⁴ takes the values 0 or 1,

R ⁷ means a phenyl or heterocyclic ring which may be substituted by at least one substituent selected from fluorine, chlorine, bromine and from alkyl groups with one to four carbon atoms, and

And means a carbon atom or nitrogen.

In one embodiment of the invention, the compounds of formula (I) or formula (Ia) are compounds in which

X, which may be the same or different, means chlorine, fluorine, bromine, trifluoromethyl, difluoromethyl, fluoromethyl groups, nitro groups, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, 2-methylpropyl groups, methoxy groups, ethoxy groups, propoxy groups , isopropoxy groups, n-butoxy groups, tert-butoxy groups, 2-methylpropoxy groups, cyano groups, trifluoromethoxy groups, difluoromethoxy groups, fluoromethoxy groups, thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl, thio-tert-butyl 2-methylthiopropyl, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropyl-sulfinyl, butylsulfinyl, tert-butylsulfinyl, 2-methyl-propylsulfinyl, methylsulfonyl, ethylsulfonyl, propyl-sulfonyl, isopropylsulfonyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, butyl-sulfonyl, trifluoromethylthiol, trifluoromethylsulfinyl, trifluoromethylsulfonyl, hydroxyl groups, mercapto groups, amino groups, methylcarbonylamino groups, ethylcarbonylamino groups, propyl arbonilaminogruppy, isopropylcarbonyl amino group, butylcarbonylamino, tert-butylcarbonylamino, 2-methyl-propylcarbonylamino, benzoylamino, methoxycarbonyl-amino, ethoxycarbonylamino group, propoxycarbonylamino group, isopropoxycarbonylamino group, butoxycarbonylamino, tert-butoxycarbonylamino group, a 2-metilpropoksikarbonilaminogruppy, trifluoromethoxy-carbonylamino, alkylsulfonylamino atoms with one to four carbon or a haloalkylsulfonylamino group with Islom carbon atoms, from one to four,

Y, which may be the same or different, means chlorine, fluorine, bromine, iodine atoms, trifluoromethyl, difluoromethyl, fluoromethyl groups, nitro groups, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, 2-methylpropyl groups, methoxy groups, ethoxy groups , propoxy groups, isopropoxy groups, n-butoxy groups, tert-butoxy groups, 2-methylpropoxy groups, cyano groups, trifluoromethoxyl, difluoromethoxyl, fluoromethoxyl, thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl, thio-tert-butyl methyl, 2-methylthiopropyl groups, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, tert-butylsulfinyl, 2-methylpropylsulfonyl, methylsulfonyl, ethylsulfonylsulfonylpropylsulfonyl-trifylsulfonyl-sulfonylpropylsulfonyl-sulfonylphenylsulfonyl-sulfonylphenylsulfonyl , trifluoromethylsulfonyl groups, hydroxyl groups, mercapto groups, amino groups, trifluoromethylcarbonylamino groups s, methylcarbonylamino, ethylcarbonylamino, propylcarbonyl amino group, isopropylcarbonylamino, butylcarbonylamino, tert-butylcarbonylamino, 2-metilpropilkarbonilaminogruppy, 2,2,2-trihloretilkarbonilaminogruppy, benzoylamino, methoxycarbonylamino group, ethoxycarbonylamino group, propoxycarbonylamino group, isopropoxycarbonylamino group, butoxycarbonylamino, tert-butoxycarbonylamino group, a 2-methyl- propoxycarbonylamino groups, trifluoromethoxycarbonylamino groups, alkylsulfonyl minogruppy carbon atoms from one to four or galogenalkilsulfonilaminogruppy carbon atoms from one to four;

R is a methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, 2-methylpropyl or trifluoromethyl, difluoromethyl, fluoromethyl group;

m takes the values 0,1, 2 or 3,

n takes values 0, 1, 2 or 3,

G means

or means

or alternatively means the following heterocycles from G4 to G9

Where

R ¹ and R ^2, independently of each other, each means a hydrogen atom, an alkyl group with one to four carbon atoms that can be substituted, an alkenyl group with two to four carbon atoms that can be substituted, an alkynyl group with carbon atoms from two to four, which may be substituted, a cycloalkyl group with the number of carbon atoms from three to six, which may be substituted, an alkylsulfonyl group with the number of carbon atoms from one to four, halogenated alkylsulfonyl group with the number of carbon atoms from one to four or a group CH ₂ -R ⁷ or together mean an alkylene group with the number of carbon atoms from three to five,

R ³ and R ^4, independently of each other, each means a hydrogen atom, a cyano group, an alkyl group with one to four carbon atoms that can be substituted, an alkenyl group with two to four carbon atoms that can be substituted, an alkynyl group with two to four carbon atoms that can be substituted, a cycloalkyl group with three to six carbon atoms that can be substituted, or an alkoxycarbonyl group with one to four carbon atoms in the alkoxyl radical ex or together denote an alkylene group with carbon atoms from three to five,

l takes the values 1 or 2,

R ⁵ means a hydrogen atom, an alkyl group with one to four carbon atoms, a cycloalkyl group with three to six carbon atoms that may be substituted, a haloalkyl group with one to four carbon atoms, a cyano group, an alkenyl group with the number carbon atoms from two to four, alkynyl group with the number of carbon atoms from two to four, an alkylcarbonyl group with the number of carbon atoms in the alkyl residue from one to four or a CH ₂ -R ⁷ group,

R ⁶ means a formyl group, a cyano group, an alkylcarbonyl group with one to four carbon atoms in the alkyl radical, one to four alkylthiocarbonyl groups with one to four carbon atoms in the alkyl radical, one to four halogenated alkylcarbonyl groups, a haloalkylthiocarbonyl group with one to four carbon atoms in the halogenated alkyl radical; an alkylaminocarbonyl group with one to four carbon atoms in the alkyl radical pex, an alkylaminothiocarbonyl group with one to four carbon atoms in the alkyl radical, a dialkylaminocarbonyl group with two to six carbon radicals, a dialkylamino-thiocarbonyl group with two to six carbon atoms, an alkoxyaminocarbonyl group with the number carbon atoms in the alkoxyl radical of one to four, an alkoxyamino-thiocarbonyl group with the number of carbon atoms in the alkoxyl radical of one to four, an alkoxycarbonyl group with the search for carbon atoms in an alkoxyl radical of one to four, an alkoxythiocarbonyl group with the number of carbon atoms in an alkoxy radical of one to four, a thioalkoxycarbonyl group with the number of carbon atoms in a thioalkoxy radical of one to four, a thioalkoxythiocarbonyl group with the number of carbon atoms in a thioalkoxy up to four, a CO-R ⁷ group, CS-R ⁷ , an alkylsulfonyl group with one to four carbon atoms or a haloalkylsulfonyl group with one to one carbon atoms up to four or alternatively

Z, which may be the same or different, means chlorine, bromine or iodine atoms, trifluoromethyl groups, nitro groups, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, 2-methylpropyl groups, cyano groups,

k ³ takes the values 0 or 1,

k ⁴ takes the values 0 or 1,

R ⁷ means a substituted or unsubstituted phenyl ring or a heterocyclic ring selected from the group consisting of pyridyl, pyrrolidinyl, imidazolyl, triazolyl, oxadiazolyl, tetrazolyl, pyrimidinyl and triazinyl rings, which may be substituted by at least one substituent selected from fluorine atoms, chlorine, bromine, iodine and methyl, ethyl, isopropyl, n-propyl, 2-methyl-propyl, n-butyl and tert-butyl groups, and

And means a carbon atom.

Compounds of formula (I) or formula (Ia) according to the present invention have an asymmetric carbon atom and therefore have optical isomers.

Used in this case, the term "alkyl group" refers to such linear or branched alkyl groups with the number of carbon atoms from one to twelve, such as methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl group and the like, in the preferred case, this concept refers to alkyl groups with the number of atoms carbon from one to six.

As used herein, the term “haloalkyl group” refers to alkyl groups with one to twelve carbon atoms, preferably one to six or one to four carbon atoms, in which at least one hydrogen atom is substituted with halogen. Suitable haloalkyl groups are, for example, CH ₂ F, CHF ₂ , CF ₃ , CF ₂ Cl, CFCl ₂ , CF ₂ Br, CF ₂ CF ₃ , CFHCF ₃ , CH ₂ CF ₃ , CFClCF ₃ , CCl ₂ CF ₃ . CF ₂ CH ₃ , CF ₂ CH ₂ F, CF ₂ CHF ₂ , CF ₂ CF ₂ Cl, CF ₂ CF ₂ Br, CFHCH ₃ , CFHCH ₂ F, CFHCHF ₂ , CHFCF ₃ , CHFCF ₂ Cl, CHFCF ₂ Br, CH ₂ CF ₃ , CFClCF ₃ , CCl ₂ CF ₃ , CF ₂ CF ₂ CF ₃ , CH ₂ CF ₂ CF ₃ , CF ₂ CH ₂ CF ₃ , CF ₂ CF ₂ CH ₃ , CHFCF ₂ CF ₃ , CF ₂ CHFCF ₃ , CF ₂ CF ₂ CHF ₂ , CF ₂ CF ₂ CH ₂ F, CF ₂ CF ₂ CF ₂ Cl, CF ₂ CF ₂ CF ₂ Br. The halogenated alkyl unit may be substituted with at least one suitable substituent.

Used in this case, the term "alkoxygroup" refers to alkoxygroups with the number of carbon atoms from one to twelve, in the preferred case, with the number of carbon atoms from one to six or from one to four. Suitable alkoxy groups are, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or tert-butoxy group, pentyloxy group or hexyloxy group. An alkoxyl unit may be substituted with at least one suitable substituent.

Each alkyl structural unit in each group, including an alkyl group as part of its configuration, can be further defined in accordance with what is presented in the above concept of "alkyl group".

Thus, for example, an “acylamino group” is an alkylcarbonylamino group, a cyclopropylcarbonylamino group and a benzoylamino group, where the alkyl structural unit can be defined as described above for the term “alkyl group”.

The term “halogen” and each halogen structural unit in each substituted halogen group refers to fluorine, chlorine, bromine and iodine, preferably refers to fluorine, chlorine or bromine.

The term "cycloalkyl group" refers to a cycloalkyl group with a number of carbon atoms from three to eight, such as a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl group, in the preferred case, this concept refers to a cycloalkyl group with a number of carbon atoms from three to seven .

The term "alkenyl group" refers to an alkenyl group with two to five carbon atoms such as a vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl or 3-butenyl, 1-pentenyl group, in the preferred case, this concept refers to an alkenyl group with the number of carbon atoms from two to four.

The term "alkynyl group" refers to such an alkynyl group with a number of carbon atoms from two to five, such as ethynyl, propargyl, 1-propynyl, butane-3-ynyl, pentan-4-ynyl group and the like, in the preferred case, this concept refers to an alkynyl group with two to four carbon atoms.

The term “heterocyclic group” refers to a heterocyclic group with 5 or 6 cycle members including at least one heteroatom selected from nitrogen, oxygen or sulfur, and this concept also refers to a fused heterocyclic group that can be fused to benzene cycle.

Examples of heterocyclic groups include furyl, thienyl, pyrrolyl, isoxazolyl, pyrazolyl, oxazolyl, oksatiazolilnaya, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrrolidinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl, quinolyl group and the like.

The compounds of formula (I) or formula (Ia) according to the invention can be prepared, for example, by the preparation methods described below (a) to (k).

The method of obtaining (a) involves the interaction of the compounds of formula (II)

where X, R and m are as defined above, with a compound of formula (III) or formula (III-a)

Where

Y, A, G and n are as defined above,

L ¹ means a halogen atom or a haloalkylsulfonyloxy group with one to four carbon atoms.

In one embodiment of the process for producing (a), compounds of formula (II) and compounds of formula (III) or formula (III-a) are reacted in the presence of a base or in the presence of at least one metal catalyst.

The following are the preparation methods (b) and (c) for preparing compounds corresponding to formula (I) or formula (Ia) in which G represents a group —CONR ¹ R ² .

Method (b) involves reacting a compound represented by formula (IV) or formula (IV-a)

,

,

where X, Y, R, A, m and n have the above meanings,

or a compound represented by formula (V) or formula (V-a)

where X, Y, R, A, m, and n have the above meanings and L ₂ is a chlorine atom, a bromine atom, an alkylcarbonyloxy group with one to four carbon atoms in the alkyl group, an alkyloxycarbonyloxy group with one to four carbon atoms in the alkoxy group or an azolyl group,

with the compound represented by formula (VI)

where R ¹ and R ² have the above meaning, using, if necessary, a condensing agent in the presence of a base.

Method (c) comprises reacting a compound represented by formula (Ib) or formula (Ie)

where X, Y, R, R ¹ , A, m and n have the above meaning,

with a compound represented by the formula

,

,

where R ² has the above meaning and L ³ means a chlorine, bromine, iodine atom, an alkylsulfonyloxy group with one to four carbon atoms, a haloalkylsulfonyloxy group with one to four carbon atoms, an arylsulfonyloxy group or an azolyl group, if necessary, the reaction is carried out in the presence of grounds.

The following is a preparation method (g) for preparing compounds corresponding to formula (I) or formula (Ia) in which G represents a group —CSNR ¹ R ² .

Method (d) involves reacting a compound represented by formula (If) or formula (Id)

,

,

Where

where X, Y, R, R ¹ , R ² , A, m and n are as defined above, with a sulfonating agent.

The following are methods for producing (e), (e) and (g) to obtain compounds corresponding to formula (I) or formula (Ia) in which G represents a group

Method (d) involves reacting a compound represented by formula (VIII) or formula (VIII-b)

where X, Y, R, R ³ , R ⁴ , A, I, m, n and L ³ have the above meaning, with the compound represented by formula (IX)

where R ⁵ and R ⁶ have the above meaning, while if necessary, the interaction is carried out in the presence of a base.

Method (e) includes reacting a compound represented by formula (X) or formula (X-a)

where X, Y, R, R ³ , R ⁴ , R ⁵ , A, I, m and n have the above meaning, with a compound represented by the formula

,

,

where R ⁶ has the above meaning and L ⁴ means a fluorine, chlorine, bromine atom, an alkylcarbonyloxy group with one to four carbon atoms in the alkyl radical, an alkoxycarbonyloxy group with one to four carbon atoms, an azolyl group, an alkyl sulfonyloxy group with the number carbon atoms from one to four, a haloalkylsulfonyloxy group with the number of carbon atoms from one to four, an arylsulfonyloxy group, and if necessary, the interaction is carried out in the presence of Niya.

Method (g) involves reacting a compound represented by formula (Ic) or formula (Ig)

where X, Y, R, R ³ , R ⁴ , R ⁶ , A, I, m and n have the above meaning, with a compound represented by the formula

,

,

where R ⁵ and L ⁴ have the above meaning, while if necessary, the interaction is carried out in the presence of a base.

The following is a preparation method (h) for preparing compounds corresponding to the formula (I) or formula (Ia) in which G is the residue G1, G6 or G8.

Method (h) involves reacting a compound represented by formula (XIII) or formula (XIII-a)

where X, Y, A, m and n have the above meaning, with dialkoxytetrahydrofuran, 1,2-diformylhydrazine or with sodium azide and trialkyl orthoformate.

The following is a preparation method (s) for preparing compounds corresponding to formula (I) or formula (Ia) in which G represents the remainder G2.

Method (s) comprises reacting a compound represented by formula (XIV) or formula (XIV-a)

where X, Y, A, m and n are as defined above, with 1,1,3,3-tetraalkoxypropane.

The following is a preparation method (k) for preparing compounds corresponding to formula (I) or formula (Ia) in which G is the residue G2, G3, G4, G5, G6, G8 or G9.

Method (k) comprises reacting a compound represented by formula (XV) or formula (XV-a)

where X, Y, R, A, m, n and L have the above meaning, with protonated residues G2, G3, G4, G5, G6, G8 or G9, namely with G2-H, G3-H, G4-H , G5-H, G6-H, G8-H or G9-H.

In accordance with the present invention, arylpyrrolidines of the formula (I) or of the formula (Ia) exhibit high insecticidal activity.

The above-described production method (a) using, for example, 3- (3,5-dichloro-phenyl) -3- (trifluoromethyl) pyrrolidine and N- (4-bromo-2-methylbenzyl) acetamide as starting materials can be illustrated reaction equation

The method of obtaining (b) using, for example, 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitrobenzoic acid and 2-picolylamine as starting compounds can be represented reaction equation

The method of obtaining (c) using, for example, 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-N- (pyridin-2-ylmethyl) benzamide and iodo-methane as starting compounds can be represented by the following reaction equation

The method of obtaining (g) using, for example, 2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -N- (pyridin-2-ylmethyl) benzamide and Lawson reagent as starting compounds can be represented by the reaction equation

The method of obtaining (e) using, for example, 1- [4- (bromomethyl) phenyl] -3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine and benzamide as starting compounds can be represented by the reaction equation

The method of obtaining (e) using, for example, 1- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} methanamine and acetyl chloride as starting compounds can be represented by the reaction equation

The method of obtaining (g) using, for example, N- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzyl} acetamide and methyl iodide as starting compounds can be represented by the reaction equation

The method of obtaining (h) using, for example, 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] aniline and 2,5-dimethoxytetrahydrofuran as the starting compounds can be represented by the reaction equation

The method of preparation (s) using, for example, 3- (3,5-dichlorophenyl) -1- (4-hydrazinophenyl) -3- (trifluoromethyl) pyrrolidine and 1,1,3,3-tetraethoxypropane as starting compounds may be represented by the reaction equation

The method of obtaining (k) using, for example, 5- (3,5-dichlorophenyl) - [3- (trifluoromethyl) pyrrolidin-1-yl] -2-fluorobenzonitrile and 1H-1,2,4-triazole as starting compounds can be represented by the reaction equation

Many compounds of formula (II), which are the starting products in the method of obtaining (a), are new compounds obtained by the method described below. The compound corresponding to the formula (XVI)

where X, m and R are as defined above, reacts, for example, with N-benzyl-1-methoxy-H - [(trimethylsilyl) methyl] methanamine in the presence of a catalyst to form a compound according to formula (XVII)

where X, m and R have the above meaning, and then carry out the debenzylation reaction to obtain the compounds of formula (II).

Known compounds of formula (XVI) are described, for example, in "The Journal of Organic Chemistry, 1991, T. 56, pp. 736-7340"; "The Journal of Organic Chemistry, 1994, Vol. 59, pp. 2898-2901"; "Journal of Fluorine Chemistry, 1999, T. 95, pp. 167-170" and in the application for international patent No. 2005/05085216A. Such compounds can also be synthesized by methods described in these publications.

Representative examples of compounds of formula (XVI) include [1- (trifluoromethyl) vinyl] benzene, 1-chloro-3- [1- (trifluoromethyl) vinyl] benzene, 1-bromo-3- [1- (trifluoromethyl) vinyl] benzene, 1-nitro-3- [1- (trifluoromethyl) vinyl] benzene, 1-trifluoromethyl-3- [1- (trifluoromethyl) vinyl] benzene, 1,3-difluoro-5- [1- (trifluoromethyl) vinyl ] benzene, 1,3-dichloro-5- [1- (trifluoromethyl) vinyl] benzene, 1,3-difluoro-5- [1- (trifluoromethyl) vinyl] benzene, 1-fluoro-2- (trifluoromethyl) - 4- [1- (trifluoromethyl) vinyl] benzene, 1,2,3-trichloro-5- [1- (trifluoromethyl) vinyl] benzene, or 1,3-dimethyl-2-nitro-5- [1- ( trifluoromethyl) vinyl] benzene.

In the above reaction, instead of N-benzyl-1-methoxy-N - [(trimethylsilyl) methyl] methanamine, N-benzyl-1-butoxy-N - [(trimethylsilyl) methyl] methanamine or N- (butoxymethyl) can be used -N - [(trimethylsilyl) methyl] cyclohexylamine. They are also well known compounds.

Catalysts that can be used in the above reaction include trifluoroacetic acid, trimethylsilyl trifluoromethanesulfonate, iodotrimethylsilane, cesium fluoride and the like.

The above reaction can be carried out in accordance with the method described in "Chemistry Letters, 1984, 1117-1120" and "Tetrahedron Letters, 1993, 34, 3279-3282", and such deprotection reactions as debenzylation can be carried out in accordance with the method described in "Journal of the Organic Chemistry, 1984, 49, 2081" and "PROTECTIVE GROUPS in ORGANIC CHEMISTRY, THIRD EDITION, JOHN WILEY & SONS, INC."

Representative examples of compounds of formula (II) in the preparation method (a) include 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine, 3- [3,5-bis (trifluoromethyl) phenyl] -3- (trifluoromethyl) pyrrolidine, 3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl) pyrrolidine, 3- (3,5-dimethyl-4-nitrophenyl) -3- (trifluoromethyl) pyrrolidine.

Many of the compounds of formula (III) or, respectively, of formula (III-a), which are the starting compounds in the preparation method (a), are known compounds that can be prepared by methods well known in organic chemistry.

Representative examples of compounds of formula (III) and, accordingly, formula (IIIa) include N- (4-bromobenzyl) acetamide, N- (4-iodobenzyl) acetamide.

The reactions in accordance with the methods of obtaining (a), (b), (c), (d), (e), (e), (g), (h), (i) and (k) can be carried out in such a suitable diluent, such as aliphatic hydrocarbons (e.g. hexane, cyclohexane, heptane and others), aliphatic halogenated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride, dichloroethane), aromatic hydrocarbons (e.g. benzene, toluene, xylene, chlorobenzene and others), simple esters (e.g. diethyl ether, dibutyl ether, dimethoxyethane, tetrahydrofuran, dioxane and others), esters (e.g. ethyl acetate, ethyl propionate and others), amides (e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone and others), nitriles (e.g. acetonitrile, propionitrile and others), dimethyl sulfoxide, water and mixtures of these solvents.

Reactions in accordance with the methods of obtaining (a), (b), (c), (d), (e), (e), (g), (h), (i) and (k) can be carried out using such the following bases, such as alkali metal bases (e.g. lithium hydride, sodium hydride, potassium hydride, butyllithium, tert-butyl lithium, trimethylsilyllithium, lithium hexamethyl disilazide, sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, sodium acetate, acetate potassium, sodium methylate, sodium ethylate, sodium tert-butylate, potassium tert-butylate and others), organic bases (e.g. triethylamine, d isopropylethylamine, tributylamine, N-methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, 4-tert-butyl-N, N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane, imidazole and others).

The methods for producing (a), (b), (c), (d), (e), (e), (g), (h), (i) and (k) can be implemented in a wide temperature range. In general, they can be implemented at temperatures from about -78 ° C to about 200 ° C, preferably from about -10 ° C to about 150 ° C. In the preferred case, these reactions are carried out at normal pressure, although they can be carried out at high pressure or under reduced pressure. The reaction time is from 0.1 to 72 hours, preferably from 0.1 to 24 hours.

The reaction in the preparation method (a) can be carried out using suitable metal catalysts such as transition metal catalysts, for example Pd ₂ (dba) ₃ , Pd ₂ ((dba) ₃ CHCl ₃ (dba means dibenzylideneacetone), palladium diacetate, copper monoiodide or copper oxide Cu ₂ O. If necessary, reactions can be carried out using phosphine ligands such as 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene, 4,5-bis (diphenylphosphino) -9, 9-dimethyl-xanthene (xanthos), tributylphosphine and the like, or amine ligands such as 8-quinolinol, prol N, N, N-dimethylglycine and the like.

So, for example, when implementing the preparation method (a), 1 mole of a compound of formula (II) is reacted with a compound of formula (III) or formula (III-a) in an amount of 1 to 3 moles in the presence of 1 to 3 moles of base and catalytic amounts of Pd ₂ (dba) ₃ CHCl ₃ and xanthos in a diluent such as toluene, and the compound of formula (I) or formula (Ia) according to the invention is obtained.

The compounds of formula (IV) or formula (IV-a), which are used in the production method (b), are new compounds. They can be obtained as described below. A compound of formula (II) may react with a compound represented by formula (XVIII)

where Y, A, n and L ¹ have the above meaning, R ⁸ means a hydrogen atom or an alkyl group with the number of carbon atoms from one to four, with the formation of a compound represented by formula (XIX) or formula (XIX-a)

where X, Y, R, A, m, n and R ⁸ are as defined above. When R ⁸ is an alkyl group with one to four carbon atoms, the compounds of the above formula (XIX) or the formula (XIX-a) can be hydrolyzed and converted to the compounds of the formula (IV) or the formula (IV-a).

The compounds of formula (XVIII) are known, for example, the following compounds are included: 4-iodobenzoic acid methyl ester, 4-bromo-2-methylbenzoic acid methyl ester, 2-fluoro-4-iodobenzoic acid ethyl ester, 2 methyl ester -chloro-4-iodobenzoic acid, 2-bromo-4-iodobenzoic acid methyl ester, 4-fluoro-2-nitrobenzoic acid methyl ester and 4-fluoro-2- (trifluoromethyl) benzoic acid ethyl ester.

The compounds of formula (IV) or formula (IV-a), which are the starting products for the preparation method (b), are well known compounds.

For example, a compound of formula (IV) or formula (IV-a) can be readily prepared by a method comprising reacting with a chlorinating reagent such as thionyl chloride, oxalyl chloride or phosphorus pentachloride, or by a method comprising reacting an organic halide such as pivaloyl chloride, or also by a method comprising reacting with carbonyldiimidazole or with sulfonyldiimidazole.

Representative examples of the compounds of formula (IV) or, respectively, of formula (IV-a) in the preparation method (b) include 4- [3- (3,5-dichlorophenyl) -3- (trifluoro-methyl) pyrrolidin-1- il] benzoic acid, 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitrobenzoic acid, 4- {3- [3,5-bis (trifluoromethyl) phenyl] -3- (trifluoromethyl) pyrrolidin-1-yl} -2-nitrobenzoic acid, 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2- (trifluoromethyl) benzoic acid and the like.

Representative examples of compounds of formula (V) or, respectively, of formula (Va) include 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzoyl chloride, 4- [3- (3,5-Dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-benzoyl chloride, 4- {3- [3,5-bis (trifluoromethyl) phenyl] -3- (trifluoromethyl) pyrrolidin- 1-yl} -2-nitrobenzoyl chloride and the like.

The compounds of formula (VI), which are the starting compounds in the preparation process (b), are well known compounds.

Representative examples include methylamine, ethylamine, cyclopropylamine, propargylamine, 2,2,2-trifluoroethylamine, 2-picolylamine, 3-aminomethyl-6-chloropyridine and the like.

The reaction corresponding to the preparation method (b) can be carried out in the presence of the following condensing reagents: 1,3-dicyclohexylcarbodiimide, 1-ethyl-3- (3'-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, diethyl cyano phosphate, 2-chloro-1-methylpyridinium iodide (Mukuyama reagent) and the like.

So, for example, when implementing the preparation method (b), 1 mole of a compound of formula (IV) or formula (IV-a) is reacted with a compound of formula (VI) in an amount of from 1 to 3 moles, using from 1 to 3 moles of a condensing reagent, in the presence, if necessary, of a catalytic amount of an additive such as 1-hydroxybenzotriazole in a diluent (for example, dimethylformamide), and the corresponding compound of formula (I) or formula (Ia) is obtained.

The compounds of formula (I-b) or formula (I-e), which are the starting products in the preparation method (c), are included in the formula (I) or formula (Ia) corresponding to the invention, they are obtained by the method (b).

The compounds of formula (VII), which are the starting products, are well-known compounds, special examples include iodomethane, iodoethane and the like.

So, for example, when implementing the preparation method (c), 1 mole of a compound of formula (Ib) or formula (Ie) is reacted with a compound of formula (VII) in an amount of 1 to 5 moles in the presence of a base in a diluent (for example, tetrahydrofuran) and receive the corresponding compound of formula (I) or formula (Ia).

The compounds of formula (If) or formula (Id), which are the starting products in the production method (d), are included in the formula (I) or formula (Ia) corresponding to the invention, they are prepared by the above method (b) or (c).

The sulfonating reagents used in the manufacturing process (d) may be phosphorus pentasulfide, Lawson's reagent and the like.

When implementing the preparation method (g), 1 mol of the compound of general formula (If) or formula (Id) can react, for example, with Lawson's reagent in an amount of from 0.5 to 3 moles in a diluent (for example, toluene) and turn into the corresponding compound formula (I) or formula (Ia).

The compounds of formula (VIII) or formula (VIII-b), which are the starting compounds in the preparation process (d), are new compounds; they can be synthesized as follows. The compound of the above formula (XIX) or formula (XIX-a) can be reduced to form compounds represented by formula (XX) or formula (XX-a)

where X, Y, R, A, m and n have the above meaning, which can then participate in such conventional reactions as halogenation or alkyl sulfonation, and are converted to compounds represented by the formula (VIIIa) or (VIII-c)

where X, Y, R, A, m, n and L ³ have the above meaning.

Representative examples of the compounds of formula (VIII) and, accordingly, of formula (VIII-b) in the preparation method (e) are 1- [3-chloro-4- (chloromethyl) phenyl] -3- (3,5-dichlorophenyl) -3 - (trifluoromethyl) pyrrolidine, 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzylmethanesulfonate, 1- [3-bromo-4- (chloromethyl) phenyl] -3- (3,5-Dichlorophenyl) -3- (trifluoromethyl) pyrrolidine and the like.

The compounds of formula (IX), which are the starting materials in the preparation process (e), are well known compounds, representative examples of these substances include acetamide, propionamide, benzamide, 2-chlorobenzamide, 3-chlorobenzamide, 4-chlorobenzamide and the like.

When implementing the preparation method (e), 1 mol of a compound of formula (VIII) or formula (VIII-b) can react, for example, with a compound of formula (IX) in an amount of 1 to 3 moles in the presence of a base in a diluent (for example, tetrahydrofuran) and converted into the corresponding compound of formula (I) or formula (Ia).

The compounds of formula (X) or formula (X-a), which are the starting compounds in the production method (e), are new compounds; they can be prepared by reacting a compound of formula (VIII) or formula (VIII-b) with a compound of formula R ⁵ NH ₂ (XXI), where R ⁵ is as defined above.

Compounds of formula (X) or formula (Xa), where 1 is 1, can also be synthesized by an alternative method, comprising reacting a compound of the above formula (II) with a compound represented by the formula (XXII)

where Y, A, R ³ , R ⁴ , n and L ¹ have the above meaning, with the formation of a compound represented by formula (XXIII) or formula (XXIII-a)

where X, Y, R, A, m, n, R ³ and R ⁴ have the above meaning, which further reacts according to the Gabriel reaction.

The compounds of the above formula (XXII) are known compounds, including 2- (4-bromobenzyl) -1H-isoindole-1,3 (2H) -dione, 2- (4-bromo-2-nitrobenzyl) -1H -isoindole-1,3 (2H) -dione, 2- (4-iodobenzyl) -1H-isoindole-1,3 (2H) -dione, 2- (4-iodo-2-nitrobenzyl) -1H-isoindole-1 , 3 (2H) -dione, 2- (4-iodo-2-chlorobenzyl) -1H-isoindole-1,3 (2H) -dione.

Compounds of formula (X) or formula (X-a), where R ³ , R ⁴ and R ⁵ are hydrogen atoms, can be easily synthesized by an alternative method, which is a conventional reduction reaction of a nitrile compound of formula (XXIV) or formula (XXIV-a )

where X, Y, R, m and n are as defined above.

The compounds of formula (XXIV) or formula (XXIV-a) are new compounds that can be obtained as shown in the following synthesis example 8.

Representative examples of compounds of formula (X) and, accordingly, formula (X-a) in the production method (e) include 1- {2-chloro-4- [3- (3,5-dichlorophenyl) -3-trifluoromethyl) pyrrolidine- 1-yl] phenyl} methanamine, 1- {2-bromo-4- [3- (3,5-dichlorophenyl) -3-trifluoromethyl) pyrrolidin-1-yl] phenyl} methanamine and the like.

The compounds of formula (XI), which are starting materials in the production method (e), are well known compounds, in particular, acetyl chloride, propionyl chloride, benzoyl chloride, 2-chlorobenzoyl chloride, 3-chlorobenzoyl chloride, 4-chlorobenzoyl chloride, nicotinoyl chloride and the like are examples thereof. .

When implementing the preparation method (e), 1 mol of a compound of formula (X) or formula (X-a) can react, for example, with a compound of formula (XI) in an amount of 1 to 3 moles in the presence of a base in a diluent (for example, tetrahydrofuran) and converted into the corresponding compound of formula (I) or formula (Ia).

The compounds of formula (Ic) or formula (Ig), which are the starting products in the production method (g), are included in the formula (I) or formula (Ia) corresponding to the present invention, and are prepared by the above method (e) or method (e) .

The compounds of formula (XII), which are starting materials, are well known, in particular, examples thereof include iodomethane, iodoethane, acetyl chloride and the like.

When implementing the preparation method (g), 1 mol of a compound of formula (Ic) or formula (Ig) can react, for example, with a compound of formula (XII) in an amount of 1 to 3 moles in the presence of a base in a diluent (for example, tetrahydrofuran) and turn into the corresponding compound of formula (I) or formula (Ia).

The compounds of formula (XIII) or formula (XIII-a), which are the starting compounds in the production method (h), are new compounds; they can be obtained as described below.

In particular, a compound of the above formula (II) is reacted with a compound represented by the formula (XXV) or the formula (XXV-a)

where Y, A, n, and L ¹ are as defined above, to form a compound of formula (XXVI) or formula (XXVI-a)

where X, Y, R, A, m and n have the above meaning, which are then reduced to obtain a compound of formula (XIII) or formula (XIII-a). Specific examples of compounds of formula (XXV) and formula (XXV-a) include 4-nitro-2-fluorobenzene, 2-bromo-4-nitrobenzene, 2-iodo-4-nitrobenzene, 2-bromo-4-fluoronitrobenzene, 2-methyl -4-fluoronitrobenzene and the like.

Representative examples of compounds of formula (XIII) and, accordingly, formula (XIII-a), in the method for producing (h) are 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl ] aniline, 2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] aniline and the like.

Dialkoxytetrahydrofurans, which are the starting materials in the production process (h), are known compounds, examples of which, in particular, are 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran and the like.

When implementing the above method of producing (h), 1 mol of the compound of formula (XIII) or formula (XIII-a) can, for example, be reacted with 2,5-dimethoxy-tetrahydrofuran in an amount of from 1 to 5 moles in a solvent (for example, in acetic acid) to form a compound of formula (I) or formula (Ia) according to the present invention.

When using this reaction in the preparation method (h) involving 1,2-diformyl hydrazine, it can be carried out in the presence of a base and trialkyl halosilane.

Organic bases such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, 4-tert-butyl-N, N-dimethylaniline, pyridine, picoline, lutidine can serve as examples of the bases. , diazabicycloundecene, diazabicyclooctane, imidazole and others.

Representative examples of trialkyl halosilanes include trimethylchlorosilane, triethylchlorosilane, trimethyl bromosilane and the like.

When implementing the above method for producing (h), 1 mol of a compound of formula (XIII) or formula (XIII-a) can be reacted with 1,2-diformylhydrazine in an amount of 1 to 5 moles in the presence of a base in an amount of 1 to 10 moles and trialkyl halosilane in an amount of from 1 to 25 moles in a large excess of pyridine with the formation of the target compound of formula (I) or formula (Ia).

In the case of the reaction of sodium azide with trialkyl orthoformate, in the framework of the process for producing (h), trialkyl orthoformates may be represented, for example, by trimethyl orthoformate, triethyl orthoformate and the like.

When implementing the method for producing (h), 1 mol of the compound of formula (XIII) or formula (XIII-a) can react with sodium azide in an amount of 1 to 3 moles and with trialkyl orthoformate in an amount of 1 to 10 moles in a diluent (for example, in acetic acid) to form a compound of formula (I) or formula (Ia) according to the invention.

The compounds of formula (XIV) or formula (XIV-a), which are the starting compounds in the preparation method (s), are new compounds prepared by the process described below. In particular, in order to obtain a compound of formula (XIV) or formula (XIV-a), a compound of the above formula (XIII) or formula (XIII-a) is reacted according to the scheme of the Sandmeyer reaction known in the field of organic chemistry, followed by reduction.

Representative examples of compounds of formula (XIV) and, respectively, of formula (XIV-a) include 3- (3,5-dichlorophenyl) -1- (4-hydrazinophenyl) -3- (trifluoromethyl) pyrrolidine, 3- (3,5 -dichlorophenyl) -1- (4-hydrazino-3-methylphenyl) -3- (trifluoromethyl) pyrrolidine and the like.

The 2,5-dialkoxytetrahydrofurans used as starting compounds in the preparation method (s) are known compounds, representative examples of which include 1,1,3,3-tetramethoxypropane, 1,1,3,3-tetraethoxypropane and the like.

When implementing the preparation method (s), 1 mol of the compound of formula (XIV) or formula (XIV-a) can be reacted, for example, with 1,1,3,3-tetraalkoxypropane in an amount of from 1 to 5 moles with the addition of, if necessary, a catalytic amount an acid such as sulfuric acid in a diluent (for example ethanol) to form a compound of formula (I) or formula (Ia) according to the invention.

The compounds of formula (XV) or formula (XV-a), which are the starting compounds in the preparation method (k), are new compounds that can be prepared by the process described below. In particular, a compound of the above formula (II) reacts with a compound of the following formula (XXVII) or formula (XXVII-a)

where Y, A, n, and L ¹ are as defined above, to form a compound of formula (XV) or formula (XV-a).

Special examples of the compounds of the above formula (XXVII) and, respectively, of the formula (XXVII-a) are 5-iodo-2-fluorobenzonitrile, 5-bromo-2-fluorobenzonitrile 4-iodo-2-nitro-1-chlorobenzene, 1,4 dibromobenzene, 1,4-diiodobenzene and the like.

Representative examples of the compounds of formula (XV) and, accordingly, of formula (XV-a) in the preparation process (k) are 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] - 2-fluorobenzonitrile, 5- {3- [3,5-bis (trifluoromethyl) phenyl] -3- (trifluoromethyl) pyrrolidin-1-yl} 2-fluorobenzonitrile and the like.

Many of the compounds represented by the formulas G2-H, G3-H, G4-H, G5-H, G6-H, G8-H, G9-H, which are the starting products in the preparation process (k), are known compounds. Special examples of such compounds include 1H-imidazole, 1H-pyrazole, 4-methyl-1H-pyrazole, 4-fluoro-1H-pyrazole, 4-chloro-lH-pyrazole, 4-bromo-1H-pyrazole, 4-iodo-1H -pyrazole, 4-nitro-1H-pyrazole, 4-methyl-1H-pyrazole, 3-trifluoromethyl-1H-pyrazole, 4-trifluoromethyl-1H-pyrazole, 4-cyano-1H-pyrazole, 1H-1,2,3 triazole, 1H-1,2,4-triazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5- (methylthio) -1H-tetrazole and the like.

When implementing the preparation method (k), 1 mol of the compound of formula (XV) or formula (XV-a) can react, for example, with G6-H in an amount of from 1 to 3 moles in the presence of 1 to 3 moles of base in a diluent (for example, in dimethylformamide) to form a compound of formula (I) or formula (Ia) according to the invention.

In the methods for preparing the compounds of formula (I) or formula (Ia) corresponding to the present invention, new products among the compounds that are raw materials (starting and intermediate products) can be represented in general form by the following formulas.

Formula (II-a)

where X has the above meaning. T ¹ is a hydrogen atom or a benzyl group, Hal-R is a haloalkyl group and p is 1, 2, 3, 4 or 5.

Formula (XVI-a)

where T ² and T ³ independently from each other mean alkyl groups.

Compounds of formula (XXVIII) or compounds of formula (XXVIII-a)

where X, Y, R, A, m and n have the above meanings, T ⁴ means groups

a cyano group, an amino group or a nitro group, R ⁸ , L ² , L ³ , R ³ , R ⁴ and R ⁵ have the above meanings.

Compounds corresponding to the present invention have high insecticidal and acaricidal activity. As a result, the compounds represented by the formula (I) or formula (Ia) according to the invention can be used as insecticides and / or acaricides. In particular, they can be used in the field of agriculture. Compounds corresponding to the present invention also show the ability to appropriately control the number of harmful insects, while not being phytotoxic to beneficial plants. In addition, the compounds of the present invention can be used to control a wide variety of pests, including, for example, harmful sucking insects, biting insects and other plant pests, pests in grain stores and pests that violate hygiene requirements, as well as pests in areas of veterinary medicine; they can be used to control their numbers, in particular for their destruction and eradication. In accordance with this, the scope of the claims of the present invention also includes a method of pest control.

The following are examples of such insect pests.

Beetles such as Azuki bean pest (Callosobruchus Chinensis), corn weevil (Sitophilus zeamais), red flour beetle (Tribolium Castaneum), large 28-point ladybug (Epilachna vigintioctomaculata), wireworm (Agriotes fuscicollis pest) rufocuprea), Colorado potato beetle (Leptinotarsa decemlineata), Diabrotica spp., Japanese pine sawfly (Monochamus altematus), rice weevil (Lissorhoptrus oryzophilus), wood rodents (Lyctus bruneus), pumpkin leaf beetle eater (Aulac).

Lepidoptera pests such as unmatched silkworm (Lymantria dispar), ringed coconut (Malacosoma neustria), white mushroom (Pieris rapae), common scoop (Spodoptera litura), cabbage scoop (Mamestra brassicae), rice fire (Chilo suppressoris) (Pyrausta nubilalis), dried fruit moth (Ephestia cautella), reticulatus (Adoxophyes orana), apple moth (Carpocapsa pomonella), spring scoop (Agrotis fucosa), wax moth (Galleria mellonella), cabbage moth (Plothis mothella) Heliothis virescens), a citrus mining moth (Phyllocnistis citrella).

Semi-winged pests such as green rice cicadas (Nephotettix cincticeps), brown rice cicadas (Nilaparvata lugens), Comstock worm (Pseudococcus comstocki), eastern citrus insect shield (Unaspis yanonensis), green peach fruit ), cotton aphid (Aphis gossypii), cabbage aphid (Phopalosiphum pseudobrassicas), pear lace (Stephanitis nashi), Nazara (Nazara spp.), greenhouse whitefly (Trialeurodes vaporariorm), Pshylla spp.

Thripsy pests such as palm thrips (Thrips palmi), western flower thrips (Frankliniella occidentalis).

Orthopterans such as the red cockroach (Blatella germanica), the American cockroach (Periplaneta americana), the African bear (Gryllotalpa africana), and the locust migratory (Locusta migratoria migratoriaodes).

Such pests from the isopter group, such as Japanese underground termite (Reticulitermes speratus), termite (Coptotermes formosanus).

Dipteran pests such as housefly (Musca domestica), yellow fever mosquito (Aedes aegypti), sprout fly (Hylemia platura), common mosquito (Culex pipiens), anopheles mosquito (Anopheles sinensis), mosquito Culex trita seniorhychus, American clover trifolii).

Mites such as (Tetranychus cinnabannus), spider mites (Tetrahychus urticae), red citrus mites (Panonychus citri), pink citrus mites (Aculops pelekassi), Tarsonemus mites (Tarsonemus spp.).

Nematodes such as potato gall nematode (Meloidogyne incognita), pine tree nematode (Bursaphelenchus lignicolus Mamiya et Kiyohara), rice nematode (Aphelenchoides besseyi), soybean cyst nematode (Heterodera glycines), meadow nematodes.

From a group of lice (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.

In addition, the compounds of the invention have a combination of good tolerance by plants, low toxicity to warm-blooded animals, they are environmentally friendly and suitable for protecting plants and their organs, for increasing yields, for improving the quality of harvested crops and for fighting animals pests, in particular with insects, arachnids, helminths, nematodes and mollusks that are found in agriculture, in horticulture, when keeping pets, in forestry ve, in parks and places of rest, in the field of protection of stored products and materials, in the field of hygiene and veterinary medicine. They can be successfully used as plant protection products. They are active towards species with normal sensitivity and resistant species, as well as at each stage of development and at all stages of development. Pests that can be controlled using the compounds and compositions of the invention, along with others, are those listed below.

In accordance with the present invention, substances with insecticidal activity against disease vectors, including all such pests, also relate to insecticides.

If necessary, the compounds of the invention in certain concentrations or in certain practical methods of application can be used as herbicides, antidotes, growth regulators or active substances to improve the properties of plants, or as microbicides, for example as fungicides, antimycotics, bactericides, antiviral agents (including active substances against viroids) or as active substances against mycoplasmic organisms and organisms, analogue egg rickettsia. If necessary, they can also be used as starting materials or precursors of other active compounds.

In the field of veterinary medicine, the new compounds of the invention can be effectively used against various harmful parasitic animals (endoparasites and ectoparasites), including insects and worms.

Examples of such animal parasites are represented by pests such as gadfly, (Gastrophilus spp.), Fly fly (Stomoxys spp.), Lice (Trichodectes spp.), Bedbugs Rhodnius (Rhodnius spp.), Dog fleas (Ctenocephalides canis), bed bug ( Cimx lecturius), cat fleas (Ctenocephalides felis), sheep meat fly (Lucilia cuprina) and the like.

As noted above, in the field of veterinary medicine, that is, in the field of veterinary medicine, the active compounds of the present invention are active against animal parasites, in particular against ectoparasites or endoparasites. The term endoparasites includes in particular helminths such as cestodes, nematodes or trematodes, and protozoa such as coccidia. Ectoparasites in a typical and preferred case are arthropods, in particular insects such as flies (with a piercing and licking mouth apparatus), parasitic larvae of lice, lice, hair lice, bird lice, fleas and others, or ticks such as common mites, for example, hard mites or soft mites, or mites such as scabies mites, red-body mites, bird mites, and others.

The following are such parasites.

The active substances according to the invention are also well suited for combating arthropods, helminths and protozoa that parasitize or infect warm-blooded animals. Preference is given to combating arthropods. Particular preference is given to insect control. Particular preference is also given to combating ticks.

Animals that can be treated to control parasites are birds, insects and, above all, mammals. Such animals include agricultural livestock, for example cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, chickens, fur animals, turkeys, ducks, geese, farmed fish, honey bees. In addition, such animals are also domestic animals and domesticated animals, for example dogs, cats, ferrets, caged birds, aquarium fish, reptiles, and those related to experimental animals, such as hamsters, guinea pigs, rats and mice.

In the fight against these arthropods, helminths and / or protozoa, the task is to reduce the mortality of the animals being processed, increase productivity (in this case, meat, milk, wool, skin and fur, eggs, honey, etc.) and improve the state of health so as to make the keeping of animals more economical and simple by using the compounds of the invention.

So, for example, it is necessary to prevent and stop the loss of blood, protecting the host animal from parasites (by application). Pest control should also help prevent the transmission of infections.

Used in this case, the concept of "fighting", referring to the field of veterinary medicine, means that the active compounds effectively provide a reduction in the degree of damage by the corresponding parasites of the animals they attack to a safe level. In particular, the term “fight” as used here means that the active compound effectively destroys the corresponding parasite, inhibiting its development or preventing its increase in numbers.

The active compounds of the present invention, when used as insecticides, can be converted into conventional formulations. Such formulations include, for example, solutions, emulsions, wettable powders, water dispersible granules, suspensions, dusts, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active substances, microcapsules, seed coating agents, compositions using the principle of combustion (these include, for example, cartridges for fumigation and smoke formation, cans and spirals), and compositions for ultra-low volume application (cold fog, hot fog).

The active compounds of formula (I) or formula (Ia) according to the invention can be formulated in commercially available formulations and ready-to-use formulations derived from these formulations which are mixed formulations with other active compounds such as insecticides that are toxic baits, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, etc. The above insecticides may include, for example, organophosphorus compounds, carbamate compounds, carboxylate chemicals, chemical agents of the chlorohydrocarbon type, insecticidal substances of microbiological origin and the like.

These formulations can be prepared by known methods. For example, they can be prepared by mixing the active substances with diluents, i.e. with liquid solvents or carriers, with diluents or carriers in the form of liquefied gases, with solid diluents or carriers, using, as appropriate, surfactants, i.e. emulsifiers and / or dispersing agents and / or blowing agents.

If water is used as a diluent, for example, organic solvents can also be used as solubilizers.

Liquid solvents can be, for example, aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons (e.g. chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons (e.g. cyclohexane or paraffins (e.g. petroleum distillation products)), alcohols (e.g. butanol, glycol and their ethers and esters), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), solvents with at sokoy polarity (e.g., dimethylformamide, dimethyl sulfoxide, etc.), water and the like.

Liquefied gas diluents or carriers can include substances that are in a gaseous state at ordinary temperature and at normal pressure, for example, aerosol propellants such as furan, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons.

Solid diluents may include, for example, ground natural minerals (e.g., kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or ciliates, etc.), ground synthetic minerals (e.g. finely divided silicic acid, alumina, silicates etc.) and similar materials.

Solid granule carriers may include, for example, crushed and fractionated natural minerals (e.g. calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules from inorganic or organic powders, and fine particles from organic materials (e.g. sawdust, coconut shells, corncobs, hemp stalks, etc.).

Emulsifying and / or foaming agents can be, for example, nonionic and anionic emulsifiers (for example, polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols (for example, alkyl aryl polyglycol ethers), alkyl sulfonates, alkyl sulfates, arylsulfonates, etc.), as well as protein hydrolysates and others.

Dispersing agents may be, for example, lignin sulphite liquor and methyl cellulose and the like.

Adhesive agents such as carboxymethyl cellulose, natural or synthetic polymers (e.g. gum arabic, polyvinyl alcohols, polyvinyl acetates, etc.) and the like can also be used in formulations (in powders, granules, emulsions).

Coloring agents such as inorganic pigments (e.g., iron oxide, titanium oxide, blue ferrocyanides, etc.), organic pigments (e.g., alizarin dyes, azo dyes or metallophthalocyanine dyes), as well as trace elements (e.g., iron salts) can be used. , manganese, boron, copper, cobalt, molybdenum, zinc, etc.).

The content of the active substances described above in such formulations can generally be from 0.1 to 95 mass. %, in the preferred case, from 0.5 to 90 mass. %

Compounds corresponding to the present invention can be used by conventional methods consistent with the formulations intended for application. It is understood that the compounds of the invention may also be present in compositions containing other ingredients such as excipients or active ingredients. One of ordinary skill in the art can select from a number of the above and known ingredients that can be expected to improve properties considered to be preferred in accordance with the intended practice.

In accordance with the invention, all plants and all parts of plants can be treated. In the context of the present invention, the concept of plants refers to all plants and to all plant populations, including both desirable and undesirable wild plants or fruit-bearing plants (they also include fruit-bearing wild plants). Cultivated plants can be plants that can be obtained as a result of conventional breeding cultivation and optimization methods, or biotechnological methods and methods using genetic engineering, as well as combinations of these methods; we can talk about transgenic plants, including plant crops that can be protected by the rights of breeders or which cannot be protected in this way. The concept of plant parts should be applied to all above-ground and underground parts and organs of plants, for example, to shoot, leaf, flower, and root, for example, leaves, needles, stems, trunks, flowers, fruiting bodies, fruits, and seeds , roots, tubers and rhizomes. Parts of plants also include harvested crops, as well as vegetative and generative planting material, such as cuttings, tubers, rhizomes, branches and seeds.

The treatment of plants and parts of plants with active substances according to the invention is carried out directly or by acting on their environment, habitat or storage area using conventional processing methods, for example by dipping, spraying, evaporation, aerosol exposure, spraying, brushing, injection methods, and in the case of planting material, in particular seeds, also by applying single-layer or multi-layer coatings.

As mentioned above, in accordance with the invention, all plants and all parts thereof can be treated. In a preferred embodiment, wild-growing or obtained by such conventional biological breeding methods as crossbreeding or fusion of protoplasts, plant cultures or parts thereof are to be processed. In another preferred embodiment, it is possible to process transgenic plants and plant varieties obtained by genetic engineering methods (GMOs, genetically modified organisms), which, if appropriate, can be combined with conventional methods, as well as parts of plants. The concept of “parts” or, respectively, “parts of plants” or “plant parts” was discussed above.

In particular, it is preferred that plant varieties that are commercially available or widely used are treated in accordance with the invention. When talking about plant varieties, they mean plants with new properties (“distinctive features”) that are grown both by conventional breeding methods, and by means of mutagenesis or techniques involving recombinant DNA. These may be varieties, biotypes and genotypes.

Depending on the type of plant or plant variety, its place of growth and growing conditions (soil, climate, growing season, top dressing), as a result of the treatment according to the invention, superadditive (“synergistic”) effects may also appear. For example, the result of this may be reduced consumption rates and / or expansion of the activity spectrum, and / or increased action of the substances and compositions used in accordance with the invention, improved plant growth, improved resistance to elevated or low temperatures, improved resistance to drought or salts in water and in soil, improved flowering, easier harvesting, faster ripening, higher yields, better quality and / or increased nutritional value of the products obtained, mproving storage stability and / or processability grown produce, which exceed the expected effects.

In a preferred case, the plants transformed in accordance with the invention transgenic (obtained by genetic engineering) or, respectively, plant varieties include all plants which, as a result of genetic modification, have obtained genetic material that gives these plants particularly outstanding valuable properties. Examples of such properties are improved plant growth, improved resistance to elevated or low temperatures, improved resistance to drought or to the salt content of water or soil, improved flowering, simplified harvesting, accelerated ripening, increased yield, improved quality and / or increased nutritional value of the grown products, increased storage stability and / or improved processability of the grown products. Other properties that are emphasized are the increased resistance of plants to pests represented by animals and microorganisms, for example, against insects, ticks, phytopathogenic fungi, bacteria and / or viruses, as well as the increased resistance of plants to certain herbicidal active compounds. As examples of transgenic plants, it is worth highlighting such important cultivated plants as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, canola, and fruit plants ( with fruits such as apples, pears, citrus fruits and grapes), especially corn, soy, potatoes, cotton, tobacco and canola. Among the properties acquired in this case, the increased resistance of plants to insects, arachnids, nematodes, slugs and snails due to toxins formed in plants, in particular, those that are formed in plants based on genetic material from Bacillus Thuringiensis (for example, based on the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF, as well as on the basis of their combinations) (such plants are referred to as Bt plants). Such particularly distinguished properties include the increased resistance of plants to fungi, bacteria and viruses as a result of acquired systemic resistance, the presence of systemin, phytoalexins, elicitors and resistance genes and, accordingly, the proteins and toxins they express. Of these distinctive properties, it is worth highlighting the increased resistance of plants to certain herbicidal active compounds, for example, imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example, this is the PAT gene). The genes providing these beneficial properties may be present in transgenic plants and in combination with each other. Examples of the “Bt plants” in question include corn varieties, cotton varieties, soybean varieties and potato varieties that are marketed under the YIELD GARD® trademarks (eg, corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton), and NewLeaf® (potato). Examples of herbicide-resistant plants in question are maize varieties, cotton varieties and soybean varieties, which are marketed under the trademarks Roundup Ready® (glyphosate resistance, for example, corn, cotton, soybeans), Liberty Link ® (resistance to phosphinotricin, for example, for rapeseed), IMI® (resistance to imidazolinones) and STS® (resistance to sulfonylureas, for example, in corn). Among the herbicide-resistant plants (their resistance to herbicides was obtained by conventional breeding methods) in question, the varieties sold under the trademark Clearfield® (for example, corn) should also be mentioned. It goes without saying that all these provisions are valid in relation to plant varieties that will only be available in the future and / or will be available for sale in the future and which will have the genetic properties listed above or obtained in the future.

In accordance with the invention, the listed plants can be successfully treated with the compounds or compositions of the invention. The above preferred range of ratios for active substances or compositions are valid for the treatment of these plants. Particular attention should be paid to the treatment of plants with compounds or compositions specially noted in this text.

It was also found that the compounds of the invention exhibit high insecticidal activity against insects that damage industrial materials.

The following are examples of insects to which special attention should be paid, but their list is not limited to this.

Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosuni, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus rucissollisollis, Lyctus ruccollollis, Lyctus ruccollollis lexicus planicollollis, Lyctus ruccollollis lexicus planollollis spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwinien-sis, Zootermopsis nevadensis, Coptotermes formosanus

Bristles such as Lepisma saccharina.

In this regard, the concept of industrial materials refers to such non-living materials as, in the preferred case, plastics, adhesive materials, adhesives, paper materials and cardboards, leather, wood and processed wood products, as well as coating compositions.

Ready-to-use compositions, if necessary, may include other insecticides and, if necessary, one fungicide or several fungicides.

If we are talking about possible additional components, then we can point to the above insecticides and fungicides.

Compounds according to the invention can also be used to protect against fouling of objects that come into contact with salt or mineralized water, in particular, these are ship hulls, protective devices, networks, buildings, berths, signaling devices.

In addition, the compounds of the invention in the form of single active substances or in combination with others can be used as anti-fouling agents.

In household use, for hygienic reasons or to protect products during storage, these active compounds are also suitable for controlling the number of animal pests, in particular insects, arachnids and ticks, which are located indoors, for example, in dwellings, in production halls, in offices, in salons of vehicles, etc. They can be used as the only active substances or in combination with other active substances and excipients in household insecticides to combat these pests. They are active both in relation to sensitive and resistant races at all stages of development. The following are listed pests.

From a squad of scorpions, for example Buthus occitanus.

From the order of ticks, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides.

From the order of spiders, for example Aviculariidae, Araneidae.

From the order of hayfields, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of two-legged millipedes, for example Blaniulus guttulatus, Polydesmus spp. From the class of the sea-footed, for example Geophilus spp.

From the order of bristles, for example Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.

From a cockroach squad, e.g., Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuligalpa,.

From a detachment of bipedal bats, for example, Acheta domesticus.

From a detachment of earwigs, such as Forficula auricularia.

From a termite group, for example, Kalotermes spp., Reticulitermes spp.

From a haying order, for example Lepinatus spp., Liposcelis spp.

From the order of beetles, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobius.

From the order of dipterans, for example, Aedes aegypti, Aedes albopictus, Aedes ta seniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila sambica ,pp. Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From a order of Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella. Tinea pellionella, Tineola bisselliella.

From a flea order, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of Hymenoptera, e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

From a group of lice, for example Pediculus humanus capitis, Pediculus humanus corporis. Pemphigus spp., Phylloera vastatrix, Phthirus pubis.

From the order of Hemoptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

In the field of home insecticides, combinations with other suitable active compounds such as phosphoric acid esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active compounds from other known classes of insecticides can be used, in particular this is even more preferred.

The compounds or compositions according to the invention, which are preferably present in suitable ready-to-use forms, can be applied in the form of aerosols using spray guns that are not pressurized, for example by means of pumps or spray nozzles, automatic aerosol generators, fog generators, in the form of foams, gels, evaporation products from cellulose or plastic plates in thermo-generators, using liquid evaporators, gel and membrane evaporators, evaporators with a fan device that does not require energy supply or, accordingly, passive evaporating systems, paper-based moth control products, in bags or as a part of moth control gels, in the form of granules or dusts, in sprayed baits or in stationary baits.

The compounds or compositions of the invention are suitable, in particular, for seed treatment. Most of the damage to beneficial plants caused by pests occurs as a result of the attack of pests already during storage and after the seeds enter the soil, during or immediately after germination of the plant germ. This is the most dangerous phase of development, since the roots and stems of a growing plant are very sensitive, and even minimal damage to them can lead to the death of the entire plant. In this regard, the protection of seeds and plant seedlings by using suitable compositions seems to be most appropriate.

Pest protection by treating plant seeds has been known for a long time and nevertheless it is an object of continuous improvement. At the same time, seed treatment entails a number of problems that cannot always be satisfactorily resolved. Accordingly, it is desirable to develop a method for protecting seeds and sprouting plants that does not require additional use of plant protection products after sowing or after germination of plants. It is also desirable to optimize the amount of active compound used so as to obtain the maximum degree of protection of seeds and germinating plants from attack by pests, but not harm the plant itself as a result of the action of the active component used. In particular, seed treatment methods should also take into account the insecticidal properties that are characteristic of transgenic plants themselves in order to obtain optimal protection for seeds and plant seedlings using a minimum amount of plant protection product.

In accordance with the foregoing, the present invention relates, in particular, to a method for protecting seeds and plant seedlings from damage by pests by treating the seeds with a composition according to the invention. The invention also relates to the use of a seed treatment composition according to the invention in order to protect seeds and plant seedlings from pests. In addition, the invention relates to seeds that have been treated with a composition according to the invention in order to protect them from pests.

One of the advantages of the present invention is, in particular, the systemic effect of the compositions of the invention; this means that treating the seeds with these compositions protects not only the seeds themselves from the pests, but also the plants that form after germination. As a result, there is no need for direct processing of plants during sowing or immediately after sowing.

In addition, it can be considered an advantage that the compositions of the invention can also be used, in particular, on transgenic seeds, from which plants expressing toxic pests are grown. When treating such seeds with the compositions of the invention, certain pests will be controlled only by expression, for example, of an insecticidal protein, and in addition, the plants will be protected from damage by the compositions of the invention.

As mentioned above, the compounds of the invention are suitable for protecting seeds of any kind of plants grown in agricultural production, in greenhouses, in forests or in the garden. In particular, this applies to crops of corn, peanuts, Canadian rapeseed, rapeseed, poppy, soybeans, cotton, beets (e.g. sugar beets and fodder beets), rice, sorghum and millet, wheat, barley, oats, rye, sunflower, tobacco potatoes and vegetables (e.g. tomatoes, cabbage plants). The compounds of the invention are also suitable for treating seeds of fruit plants and vegetables, as described above. Particular importance is attached to the processing of seeds of corn, soybean, cotton, wheat and Canadian rapeseed or ordinary rapeseed.

As noted above, the treatment of the seed composition of transgenic plants according to the invention is also of great importance. We are talking about the treatment of plant seeds, which, as a rule, have at least one heterologous gene responsible for the expression of a polypeptide with certain insecticidal properties. In this context, heterologous genes in transgenic seeds can be derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladum. The present invention can be used, in particular, for the treatment of transgenic seed, in which at least one heterologous gene is present, which originates from Bacillus spp. and which controls the formation of a substance that is active in relation to the European grain drill and / or to a pest that damages the roots of the grain. In particular, a heterologous gene derived from Bacillus thuringiensis is preferred.

In the context of the present invention, the compounds of the invention are applied to the seeds both in pure form and in the form of suitable formulations. In a preferred case, the seeds are treated in a state where they are stable enough to tolerate such treatment without damage. In general, seeds can be processed at any time from harvesting to sowing. The seeds used for this are usually already separated from the plant and freed from the cobs, shells, cuttings, shells, fibers and meaty parts of the fruit.

During seed treatment, care must be taken to ensure that the amount of the compound applied to the seeds of the invention and / or the amount of other additives is selected so that it does not adversely affect the germination of the seeds and which does not damage the resulting plant. This should be taken into account, in particular, in those cases when the active compound can have a phytotoxic effect at certain consumption rates.

The active compounds according to the invention, used against pests that violate hygienic requirements, and against pests in granaries, are characterized by good resistance to alkali on calcareous bases and exhibit excellent residual effects on wood and soil.

In addition, the active compounds of formula (I) or formula (Ia) according to the invention can be formulated with synergists; however, such formulations and ready-to-use formulations may be conventional commercially available formulations and formulations. Such synergists, which do not necessarily show activity in their pure form, are compounds that enhance the action of active compounds.

In the General case, when using the compounds of the invention for treating animals, they can be directly applied as single substances. In a preferred case, they are applied in the form of pharmaceutical compositions, which may contain pharmaceutically acceptable diluents and / or excipients, which are known in this field.

In the field of veterinary medicine and when keeping animals, the active compounds can be applied (administered) by known methods, while for enteral administration they are, for example, in the form of tablets, capsules, liquid compositions for oral administration, impregnations, granules, pastes, balls, they can be administered through a probe, in the form of suppositories; parenteral administration is, for example, injection (intramuscularly, subcutaneously, intravenously, intraperitoneally, etc.), implantation, nasal administration, transdermal administration, for example, when bathing, dipping, spraying, watering and spraying, dousing, dusting or also using accessories containing the active substance, such as collars, tail tags, bandages on the extremities, markings, etc. Active substances can be formulated such as shampoos or as appropriate formulations in aerosol containers, in spray devices that are not pressurized, for example, sprays formed by pumps or spray guns.

When used on food products, poultry, domestic animals and in such cases, the active substances corresponding to the invention can be applied in the form of compositions (for example, in the form of dusts, wettable powders, emulsions, emulsion concentrates, fluid homogeneous solutions and suspension concentrates), which contain active compounds in an amount of from 1 to 80 wt.%, while they can be applied both directly and after dilution (for example, dilutions with a ratio of from 100 to 10000), they can also be applied using a chemical second bath.

When used in the field of veterinary medicine, the active compounds of the invention can be combined with suitable synergists or with other active compounds such as, for example, acaricides, insecticides, anthelmintic drugs, drugs for protozoal infections.

In more detail, the present invention is illustrated by the following examples. However, the scope of the claims cannot be limited only by these examples.

Synthesis Example 1

Synthesis of N- {4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-methylbenzyl} -acetamide (No. 3-11)

sodium tert-butylate (0.3 g), tris (dibenzylideneacetone) dipalladium (0) (adduct with chloroform, 0.04 g) and xanthos (0.07 g) are added to the solution 3- (3,5-dichlorophenyl) - 3- (trifluoromethyl) -pyrrolidine (0.59 g) and N- (4-bromo-2-methylbenzyl) acetamide (0.5 g) in toluene under argon atmosphere and the mixture is heated for 5 hours with stirring at 80 ° C. The reaction solution was diluted with tert-butyl methyl ether and washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain H- {4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-methylbenzyl} acetamide ( 0.6 g).

¹ H-NMR (deuterochloroform) δ: 2.13-2.18 (6H, m), 2.51-2.53 (1H, m), 2.81-2.83 (1H, m) 3.45-3.56 (2H, m), 3.75-3.78 (1H, m), 4.01-4.04 (1N. M), 4.25 (1H, s .), 4.57 (1H, s.), 6.40-6.44 (2H, m.), 6.93-6.96 (1H, m.), 7.30-7.38 (3H , m.).

Synthesis Example 2

Synthesis of 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-N- (pyridin-2-ylmethyl) benzamide (No. 1-16)

Synthesis Example 2-1

Synthesis of 1-benzyl-3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (No. 5-11)

To a solution of 1,3-dichloro-5- [1- (trifluoromethyl) vinyl] benzene (6.1 g) and N-benzyl-1-methoxy-N - [(trimethylsilyl) methyl] methanamine (5.0 g) in under ice cooling, a solution of trifluoroacetic acid (0.24 g) in dichloromethane is added dropwise. After completion of the dropwise addition, the mixture was warmed to room temperature and stirred for 3 hours. The solution was concentrated under reduced pressure and the residue was diluted with tert-butyl methyl ether. The solution was washed with a saturated solution of sodium bicarbonate in water and dried over anhydrous magnesium sulfate. After that, the desiccant was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 1-benzyl-3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (5.7 g).

1 H-NMR (deuterochloroform) δ: 2.27-2.36 (1H, m), 2.53-2.62 (1H, m), 2.69-2.83 (2H, m) 3.08 (2H, dd), 3.67 (2H, s.), 7.25-7.36 (8H, m.).

Synthesis Example 2-2

Synthesis of 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (No. 5-12)

A solution of 1-benzyl-3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (5.7 g) and 1-chloroethyl chloroformate (4.4 g) in dichloroethane is heated under reflux for 3 hours. The mixture was cooled to room temperature and then concentrated under reduced pressure. Methanol was added to the resulting residue, and then 2 hours was heated with stirring at 60 ° C. The mixture is cooled to room temperature and then water is added to it. The solution was washed twice with a solvent mixture of hexane and ethyl acetate (9: 1). The solution was made alkaline with sodium bicarbonate and then extracted three times with ethyl acetate. The organic layers are combined, washed with brine and dried over anhydrous magnesium sulfate. After that, the desiccant is filtered off, the solvent is distilled off under reduced pressure to obtain 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (4.2 g).

¹ H-NMR (deuterochloroform) δ; 2.24-2.33 (1H, m), 2.51-2.56 (1H, m), 2.97-3.07 (1H, m), 3.19-3.26 ( 2H, m.), 3.74 (1H, d.), 7.25 (2H, d.), 7.35 (1H, t.).

Synthesis Example 2-3

Synthesis of methyl 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitrobenzoate (No. 4-6)

To a solution of methyl 4-fluoro-2-nitrobenzoate (1.1 g) and 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (1.5 g) in 1-methyl-2-pyrrolidinone potassium carbonate (1.5 g) and heat the mixture with stirring at 100 ° C for 2 hours. The mixture was cooled to room temperature and then poured into water, then extracted twice with ethyl acetate. The organic layers are combined, washed with water and dried over anhydrous magnesium sulfate. Then the desiccant is filtered off, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel chromatography to obtain methyl 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitrobenzoate (1, 24 g).

¹ H-NMR (deuterochloroform) δ: 2.53-2.67 (1H, m), 2.89-2.97 (1H, m), 3.50-3.71 (2H, m) 3.83 (1H, d), 3.85 (3H, s), 4.15 (1H, d), 6.69 (1H, dd), 6.75 (1H, d) .), 7.26 (2H, d.), 7.42 (1H, t.), 7.81 (1H, d.).

Synthesis Example 2-4

Synthesis of 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-benzoic acid (No. 4-7)

To a solution of methyl 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-benzoate (1.24 g) in 1,4-dioxane was added 2N. aqueous sodium hydroxide (5.4 ml) and heat the mixture with stirring at 80 ° C. The mixture is cooled to room temperature, acidified with 2 N. hydrochloric acid and then the mixture is extracted twice with ethyl acetate. The organic layers are combined, washed with water and dried over anhydrous magnesium sulfate. After the desiccant was separated by filtration, the solvent was distilled off under reduced pressure to obtain 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-benzoic acid (0.85 g).

¹ H-NMR (d6-dimethyl sulfoxide) δ: 2.58-2.72 (1H, m), 2.91-3.04 (1H, m), 3.47-3.57 (2H, m .), 3.87 (1H, d), 4.32 (1H, d), 6.86 (1H, dd), 7.04 (1H, d), 7.65 (2H d.), 7.71 (1H, t.), 7.78 (1H, d.).

Synthesis Example 2-5

Synthesis of 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-N- (pyridin-2-ylmethyl) benzamide (No. 1-16)

To a solution of 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-benzoic acid (0.3 g) and 2-picolylamine (0.07 g) in 1-ethyl-3- (3'-dimethylaminopropyl) carbodiimide hydrochloride (0.13 g) and 1-hydroxybenzotriazole monohydrate (0.01 g) were added to dimethylformamide and the mixture was stirred for 6 hours at room temperature. The reaction solution was poured into water, then extracted twice with ethyl acetate. The organic layers are combined, washed with water and dried over anhydrous magnesium sulfate. After separating the desiccant by filtration, the solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-nitro-N- (pyridine -2-ylmethyl) benzamide (0.19 g).

¹ H-NMR (deuterochloroform) δ: 2.54-2.65 (1H, m), 2.89-2.97 (1H, m), 3.51-3.67 (2H, m) 3.83 (1H, d), 4.13 (1H, d), 4.74 (2H, d), 6.75 (1H, d), 7.08 (1H, d) .), 7.15-7.23 (2H, m.), 7.28 (2H, br.s), 7.37 (1H, d), 7.41 (1H, t), 7 49 (1H, d.), 7.70 (1H, etc.), 8.52 (1H, d.).

Synthesis Example 3

Synthesis of 2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -N- (pyridin-2-ylmethyl) benzenecarbothioamide (No. 1-81)

To a solution of 2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -N- (pyridin-2-ylmethyl) benzamide (0.35 g) in toluene is added Lawson's reagent (0.28 g) and the mixture is refluxed for 3 hours. After the mixture was cooled to room temperature, the solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain 2-chloro-4- [3- (3,5-dichloro-phenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] - N- (pyridin-2-ylmethyl) benzene-carbothioamide (0.10 g).

¹ H-NMR (deuterochloroform) δ: 2.51-2.61 (1H, m), 2.84-2.92 (1H, m), 3.45-3.61 (2H, m) 3.79 (1H, d), 4.08 (1H, d), 5.08 (2H, d), 6.49-6.54 (2H, m), 7.22-7.28 (3H, m.), 7.36 (1H, d.), 7.40 (1H, t.), 7.72 (1H, d.), 7.79 (1H, d.), 8.54 (1H, d.), 9.27 (1H, br.s.).

Synthesis Example 4

Synthesis of N- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzyl} acetamide (No. 3-3)

Synthesis Example 4-1

Synthesis of 1- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} methanamine (No. 4-49)

To a solution of 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (0.4 g) and 2- (2-chloro-4-iodobenzyl) -1H-isoindole-1,3- (2H) -dione (0.69 g) in toluene, sodium tert-butylate (0.2 g), tris (dibenzylideneacetone) dipalladium (0) (adduct with chloroform, 0.03 g) and xanthos (0.05 g) are added in argon atmosphere and 3 hours heat the mixture with stirring at 80 ° C. The reaction solution was diluted with tert-butyl methyl ether and then washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give a crude product. This product was dissolved in methanol, then aqueous hydrazine (0.03 g) was added, and then the mixture was heated under reflux for 12 hours. The reaction solution was diluted with tert-butyl methyl ether and washed with brine. The organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain 1- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} methanamine (0, 12 g).

¹ H-NMR (deuterochloroform) δ: 2.47-2.54 (1H, m), 2.78-2.85 (1H, m), 3.46-3.49 (2H, m) 3.69-4.01 (4H, m.), 6.47-6.50 (1H, m.), 6.73-6.76 (1H, m.), 7.25-7.35 (4H, m.).

Synthesis Example 4-2

Synthesis of N- {2-chloro-4-3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzyl} acetamide (No. 3-3)

To a solution of 1- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} methanamine (0.12 g) and triethylamine (0.04 g ) acetyl chloride (0.02 g) is added dropwise in tetrahydrofuran and the mixture is stirred for 1 hour at room temperature. The reaction solution was diluted with tert-butyl methyl ether and then washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain N- {2-chloro-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzyl} acetamide (0, 1 g).

¹ H-NMR (deuterochloroform) δ: 1.98-2.01 (3H, m), 2.50-2.58 (1H, m), 2.82-2.87 (1H, m) 3.45-3.51 (2H, m), 3.74 (1H, d), 4.02 (1H, d), 4.41 (2H), 6.43-6.46 (1H, m.), 6.58-6.59 (1H, m.), 7.26-7.38 (4H, m.).

Synthesis Example 5

Synthesis of 1- {2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} -1H-tetrazole (No. 2-23)

Synthesis Example 5-1

Synthesis of 1- (bromo-4-nitrophenyl) -3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (No. 4-20)

To a solution of 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (1.3 g) and 2-bromo-4-fluoro-1-nitrobenzene (1.0 g) in 1-methyl-2-pyrrolidinone potassium carbonate (1.3 g) was added and the mixture was heated for 3 hours with stirring at 100 ° C. The mixture was cooled to room temperature, then poured into water and extracted twice with ethyl acetate. The organic layers are combined, washed with water and dried over anhydrous magnesium sulfate. The desiccant is filtered off, the solvent is distilled off under reduced pressure and the residue is purified by silica gel chromatography to obtain 1- (3-bromo-4-nitrophenyl) -3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (1.56 g) .

¹ H-NMR (deuterochloroform) δ: 2.53-2.66 (1H, m), 2.89-2.97 (1H, m), 3.51-3.71 (2H, m) 3.83 (1H, d), 4.16 (1H, d), 6.53 (1H, dd), 6.84 (1H, d). 7.27 (2H, br.s.), 7.42 (1H, t.), 8.07 (1H, d.).

Synthesis Example 5-2

Synthesis of 2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] aniline (No. 4-21)

Chloride dihydrate is added to a solution of 1- (3-bromo-4-nitrophenyl) -3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (1.10 g) in a mixture of solvents of 1,4-dioxane and ethanol. tin (2.05 g) and a small amount of concentrated hydrochloric acid, and then stirred for 4 hours at 90 ° C. The mixture was cooled to room temperature, poured into a solution of a mixture of ethyl acetate and water, and then neutralized with sodium bicarbonate with vigorous stirring. After filtering the precipitate through activated carbon, the organic layer was separated and the aqueous layer was extracted with ethyl acetate. The organic layers are combined, then washed with brine and dried over anhydrous magnesium sulfate. The desiccant is filtered off, the solvent is distilled off under reduced pressure and the residue is purified by silica gel chromatography to obtain 2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] aniline (0.73 g )

¹ H-NMR (deuterochloroform) δ: 2.44-2.54 (1H, m), 2.75-2.83 (1H, m), 3.32-3.50 (2H, m) 3.56-3.76 (3H, m), 3.92 (1H, d), 6.46 (1H, dd), 6.70-6.78 (2H, m) 7.29 (2H, br.s.), 7.37 (1H, t.).

Synthesis Example 5-3

Synthesis of 1- {2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} -1H-tetrazole (No. 2-23)

To a mixture of 2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] aniline (0.60 g), triethyl orthoformate (0.98 g) and sodium azide (0 , 38 g) acetic acid (1.1 g) is added and then the mixture is heated for 4 hours with stirring at 100 ° C. The mixture was cooled to room temperature and poured into water, then extracted twice with ethyl acetate. The organic layers are combined, then washed with water and dried over anhydrous magnesium sulfate. The desiccant is filtered off, then the solvent is distilled off under reduced pressure, and the residue is purified by silica gel chromatography to obtain 1- {2-bromo-4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] phenyl} -1H-tetrazole (0.52 g), mp 193-194 ° C.

Synthesis Example 6

Synthesis of 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2- (1H-1,2,4-triazol-1-yl) benzonitrile (No. 2-39)

Synthesis Example 6-1

Synthesis of 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-fluoro-benzonitrile (No. 4-17)

3- (3,5-Dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (0.6 g) and 2-fluoro-5-iodobenzonitrile (0.57 g) are dissolved in toluene and the mixture is freed of gas three times. Sodium tert-butylate (0.20 g), tris (dibenzylideneacetone) dipalladium as a complex with chloroform (0.04 g) and xanthos (0.07 g) are added to the solution in toluene in an argon atmosphere and the mixture is stirred at 80 ° C. The mixture was cooled to room temperature, diluted with ethyl acetate, washed with water and dried over anhydrous magnesium sulfate. After separating the drying agent by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-fluorobenzonitrile (0.54 g ), mp 184-186 ° С.

Synthesis Example 6-2

Synthesis of 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2- (1H-1,2,4-triazol-1-yl) benzonitrile (No. 2-39)

Sodium hydride (0.04 g) was added to a solution of 1H-1,2,4-triazole (0.06 g) in dimethylformamide under ice cooling, the mixture was warmed to room temperature and then it was stirred for 0.5 hours. To the resulting solution was added a solution of 0.30 g of 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2-fluorobenzonitrile in dimethylformamide and the mixture was heated under reflux for 6 hours. The mixture was cooled to room temperature, then it was poured into water and extracted twice with ethyl acetate. The organic layers are combined, washed with water and dried over anhydrous magnesium sulfate. After separating the desiccant by filtration, the solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain 5- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] -2- (1H-1,2 , 4-triazol-1-yl) benzonitrile (0.18 g).

¹ H-NMR (d6-dimethyl sulfoxide) δ: 2.62-2.73 (1H, m), 2.95-3.03 (1H, m), 3.49-3.55 (2H, m .), 3.90 (1H, d.), 4.31 (1H, d.), 7.09 (1H, dd), 7.29 (1H, d.), 7.61 (1H, d. .), 7.68 (2H, d.), 7.71 (1H, t.), 8.26 (1H, s.), 8.98 (1H, s.).

Synthesis Example 7

Synthesis of 1,3-dimethyl-2-nitro-5- [1- (trifluoromethyl) vinyl] benzene (No. 6-1)

5-Bromo-1,3-dimethyl-2-nitrobenzene (10.0 g), [1- (trifluoromethyl) vinyl] boronic acid (60% purity, 13.4 g) and potassium carbonate (14.4 g) are dissolved in a mixture of solvents of tetrahydrofuran and water and three times carry out an operation to remove gases. Bis (triphenylphosphine) palladium (II) dichloride (1.5 g) was added to this solution, and the mixture was heated under reflux for 3 hours under argon atmosphere. The mixture was cooled to room temperature, poured into water and extracted twice with ethyl acetate. The organic layers are combined, washed with water and dried over anhydrous magnesium sulfate. After separating the desiccant by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 1,3-dimethyl-2-nitro-5- [1- (trifluoromethyl) vinyl] benzene (11.2 g).

¹ H-NMR (deuterochloroform) δ: 2.34 (6H, s.), 5.78-5.80 (1H, m.), 6.03-6.04 (1H, m.), 7.20 (2H, s.).

Synthesis Example 8

Synthesis of 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzonitrile (No. 4-2)

To a solution of 3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidine (0.30 g) and 4-fluoro-benzonitrile (0.12 g) in dimethyl sulfoxide (DMSO) are added potassium carbonate (0.27 g) and 6 hours heat the mixture with stirring at 120 ° C. The mixture was cooled to room temperature and poured into water, which was then extracted twice with ethyl acetate. The organic layers are combined, then washed with water and dried over anhydrous magnesium sulfate. After separating the desiccant by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 4- [3- (3,5-dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-1-yl] benzonitrile (0.05 g).

¹ H-NMR (deuterochloroform) δ: 2.51-2.62 (1H, m), 2.86-2.94 (1H, m), 3.56-3.61 (2H, m), 3 80 (1H, d), 4.12 (1H, d), 6.59 (2H, d), 7.26 (2H, b.s.), 7.41 (1H, t.) 7.52 (2H, d.).

The compounds and intermediates of formula (I) or formula (Ia) according to the invention, obtained by the same methods as those described in the above synthesis examples and in accordance with the methods described above, as well as their physical characteristics are given in tables 1 to 13 Each of the synthesized compounds obtained in the above examples is also included in the corresponding table.

The following abbreviations are used in these tables.

Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph is a phenyl group, Pen is a pentyl group.

Table 1

(X) _m R Y R ¹ R ² BUT W Mp. ° C 1-1 3,5-Cl ₂ CF ₃ N CF ₃ CH ₂ N CH O 1-2 3,5-Cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-3 3,5-Cl ₂ CF ₃ CH ₃ CF ₃ CH ₂ N CH O 1-4 3,5-Cl ₂ CF ₃ CH ₃ 2-Pyridyl-CH ₂ N CH O 1-5 3,5-Cl ₂ CF ₃ F CF ₃ CH ₂ N CH O 1-6 3,5-Cl ₂ CF ₃ F 2-Pyridyl-CH ₂ N CH O 1-7 3,5-Cl ₂ CF ₃ Cl CF ₃ CH ₂ N CH O 1-8 3,5-Cl ₂ CF ₃ Cl 2-Pyridyl-CH ₂ N CH O 1-9 3,5-Cl ₂ CF ₃ Br CF ₃ CH ₂ N CH O 1-10 3,5-Cl ₂ CF ₃ Br 2-Pyridyl-CH ₂ N CH O 1-11 3,5-Cl ₂ CF ₃ Br Cyclopropyl N CH O 1-12 3,5-Cl ₂ CF ₃ Br NCCH ₂ CH ₂ N CH O 1-13 3,5-Cl ₂ CF ₃ I CF ₃ CH ₂ N CH O

(X) _m R Y R ¹ R ² BUT W Mp. ° C 1-14 3,5-Cl ₂ CF ₃ I 2-Pyridyl-CH ₂ N CH O 1-15 3,5-Cl ₂ CF ₃ NO ₂ CF ₃ CH ₂ N CH O 1-16 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-17 3-cl CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-18 3-cl CF ₃ NO ₂ CF ₃ CH ₂ N CH O 1-19 3-br CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-20 3-CF ₃ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 169-170 1-21 3-CF ₃ CF ₃ NO ₂ CF ₃ CH ₂ N CH O 1-22 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-23 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CF ₃ CH ₂ N CH O 1-24 3-NO ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 176-179 1-25 3,5-Cl ₂ CF ₃ CF ₃ 2-Pyridyl-CH ₂ N CH O 1-26 3,5-Cl ₂ CF ₃ OCH ₃ 2-Pyridyl-CH ₂ N CH O 1-27 3,5-Cl ₂ CF ₃ CN 2-Pyridyl-CH ₂ N CH O 1-28 3,5-Cl ₂ CF ₃ OCF ₃ 2-Pyridyl-CH ₂ N CH O 1-29 3,5-Cl ₂ CF ₃ SCH ₃ 2-Pyridyl-CH ₂ N CH O 1-30 3,5-Cl ₂ CF ₃ S (O) CH ₃ 2-Pyridyl-CH ₂ N CH O 1-31 3,5-Cl ₂ CF ₃ S (O) ₂ CH ₃ 2-Pyridyl-CH ₂ N CH O 1-32 3,5-Cl ₂ CF ₃ SCF ₃ 2-Pyridyl-CH ₂ N CH O 1-33 3,5-Cl ₂ CF ₃ S (O) CF ₃ 2-Pyridyl-CH ₂ N CH O 1-34 3,5-Cl ₂ CF ₃ S (O) ₂ CF ₃ 2-Pyridyl-CH ₂ N CH O 1-35 3,5-Cl ₂ CF ₃ IT 2-Pyridyl-CH ₂ N CH O 1-36 3,5-Cl ₂ CF ₃ SH 2-Pyridyl-CH ₂ N CH O 1-37 3,5-Cl ₂ CF ₃ NH ₂ 2-Pyridyl-CH ₂ N CH O 1-38 3,5-Cl ₂ CF ₃ NHCOCH ₃ 2-Pyridyl-CH ₂ N CH O

(X) _m R Y R ¹ R ² BUT W Mp. ° C 1-39 3,5-cl ₂ CF ₃ NHCOCF ₃ 2-Pyridyl-CH ₂ N CH O 1-40 3,5-cl ₂ CF ₃ NHCO ₂ CH ₃ 2-Pyridyl-CH ₂ N CH O 1-41 3,5-cl ₂ CF ₃ NHCO ₂ CH ₂ CCl ₃ 2-Pyridyl-CH ₂ N CH O 1-42 3-CH ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-43 3-OCH ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-44 3-cn CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-45 3-OSF ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-46 3-SCH ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-47 3-S (O) CH ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-48 3-S (O) ₂ CH ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-49 3-SCF ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-50 3-S (O) CF ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-51 3-S (O) ₂ CF ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-52 3-OH CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-53 3-SH CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-54 3,4-Cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-55 3,4-Cl ₂ CF ₃ N CF ₃ CH ₂ N CH O 77-80 1-56 3,4,5-Cl ₃ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-57 3,4,5-Cl ₃ CF ₃ N CF ₃ CH ₂ N CH O 1-58 3,5-Br ₂ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-59 3,5-Br ₂ CF ₃ N CF ₃ CH ₂ N CH O 1-60 3,5-Me ₂ -4-NO ₂ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-61 3,5-Me ₂ -4-NO ₂ CF ₃ N CF ₃ CH ₂ N CH O

(X) _m R Y R ¹ R ² BUT W Mp. ° C 1-62 3,5-cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N CH S 1-63 3,5-Cl ₂ CF ₃ NO ₂ N N CH O 1-64 3,5-Cl ₂ CF ₃ NO ₂ Me N CH O 1-65 3,5-Cl ₂ CF ₃ NO ₂ iso-Pr N CH O 1-66 3,5-Cl ₂ CF ₃ NO ₂ Phch ₂ N CH O 1-67 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ CO ₂ CH ₃ N CH O 1-68 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ CONMe N CH O 1-69 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ (cyclo) Pr N CH O 1-70 3,5-cl ₂ CF ₃ NO ₂ SO ₂ Me N CH O 1-71 3,5-cl ₂ CF ₃ NO ₂ SO ₂ CF ₃ N CH O 1-72 3,5-cl ₂ CF ₃ NO ₂ CH ₂ = CHCH ₂ N CH O 1-73 3,5-cl ₂ CF ₃ NO ₂ NSSSN ₂ N CH O 1-74 3,5-cl ₂ CF ₃ NO ₂ CH ₂ CN N CH O 1-75 3,5-cl ₂ CF ₃ NO ₂ C (Me) ₂ CH ₂ SCH ₃ N CH O 1-76 3,5-cl ₂ CF ₃ NO ₂ 2-f-ph N CH O 1-77 3,5-cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N CH O 1-78 3,5-cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N N O 1-79 3,5-cl ₂ CF ₃ N 2-Pyridyl-CH ₂ CH ₃ CH O 1-80 3-NO ₂ CF ₃ NO ₂ CF ₃ CH ₂ N CH O 1-81 3,5-cl ₂ CF ₃ Cl 2-Pyridyl-CH ₂ N CH S 1-82 2-C1 ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-83 2,3-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-84 3,5-cl ₂ CF ₃ NO ₂ 3-Pyridyl-CH ₂ N CH O 1-85 3,5-cl ₂ CF ₃ NO ₂ 4-pyridyl-CH ₂ N CH O

(X) _m R Y R ¹ R ² BUT W Mp. ° C 1-86 3,5-Cl ₂ CF ₃ NO ₂ 2- (6-Cl-Pyridyl) CH ₂ N CH O 1-87 3,5-Cl ₂ CF ₃ NO ₂ 3- (6-Cl-Pyridyl) CH ₂ N CH O 1-88 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyrinidyl-CH ₂ N CH O 1-89 3,5-Cl ₂ CF ₃ NO ₂ 1- (1-Ethylpyrrolidin-2-y1) -CH ₂ N CH O 1-90 3,5-Cl ₂ CF ₃ CF ₃ CF ₃ CH ₂ N CH O 1-91 3,5-Cl ₂ CF ₃ CF ₃ 2- (6-Cl-Pyridyl) -CH ₂ N CH O 1-92 3,5-Cl ₂ CF ₃ NO ₂ Me ₂ NCH = CH O 1-93 3,5-Cl ₂ CF ₃ NO ₂ EtON-CH N CH O 1-94 3,5-Cl ₂ CF ₃ C = NOSH ₃ 2-Pyridyl-CH ₂ N CH O 1-95 4-cl CF ₃ NO ₂ 2-Pyridyl-CH ₂ N CH O 1-96 4-cl CF ₃ NO ₂ CF ₃ CH ₂ N CH O 1-97 3,5-Cl ₂ CF ₃ CN CF ₃ CH ₂ N CH O 1-98 3,5-Cl ₂ CF ₃ CF ₃ N N CH O 1-99 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ 2-Pyridyl-CH ₂ N CH O 1-100 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ CF ₃ CH ₂ N CH O 1-101 3,5-cl ₂ CF ₃ N CF ₃ CH ₂ N N O 1-102 3,4,5-Cl ₃ CF ₃ CF ₃ 2-Pyridyl-CH ₂ N CH O

table 2

(X) _m R Y G Z BUT Mp ° C 2-1 3,5-Cl ₂ CF ₃ N G1 N CH 2-2 3,5-Cl ₂ CF ₃ N G2 N CH 2-3 3,5-Cl ₂ CF ₃ N G3 N CH 2-4 3,5-Cl ₂ CF ₃ N G4 N CH 2-5 3,5-Cl ₂ CF ₃ N G5 N CH 2-6 3,5-Cl ₂ CF ₃ N G6 N CH 2-7 3,5-Cl ₂ CF ₃ N G7 N CH 2-8 3,5-Cl ₂ CF ₃ N G8 N CH 2-9 3,5-Cl ₂ CF ₃ N G9 N CH 2-10 3,5-Cl ₂ CF ₃ F G6 N CH 2-11 3,5-Cl ₂ CF ₃ F G8 N CH 2-12 3,5-Cl ₂ CF ₃ F G9 N CH 2-13 3,5-Cl ₂ CF ₃ Cl G6 N CH 2-14 3,5-Cl ₂ CF ₃ Cl G8 N CH 2-15 3,5-Cl ₂ CF ₃ Cl G9 N CH 2-16 3,5-Cl ₂ CF ₃ Br G1 N CH 2-17 3,5-Cl ₂ CF ₃ Br G2 N CH 2-18 3,5-Cl ₂ CF ₃ Br G3 N CH

(X) _m R Y G Z BUT Mp. ° C 2-19 3,5-Cl ₂ CF ₃ Br G4 N CH 2-20 3,5-Cl ₂ CF ₃ Br G5 N CH 2-21 3,5-Cl ₂ CF ₃ Br G6 N CH 2-22 3,5-Cl ₂ CF ₃ Br G7 N CH 2-23 3,5-Cl ₂ CF ₃ Br G8 N CH 193-194 2-24 3,5-Cl ₂ CF ₃ Br G9 N CH 2-25 3,5-Cl ₂ CF ₃ I G6 N CH 2-26 3,5-Cl ₂ CF ₃ I G8 N CH 2-27 3,5-Cl ₂ CF ₃ I G9 N CH 2-28 3,5-Cl ₂ CF ₃ Me G6 N CH 2-29 3,5-Cl ₂ CF ₃ Me G8 N CH 2-30 3,5-Cl ₂ CF ₃ CF ₃ G6 N CH 2-31 3,5-Cl ₂ CF ₃ CF ₃ G8 N CH 2-32 3,5-Cl ₂ CF ₃ NO ₂ G6 N CH 2-33 3,5-Cl ₂ CF ₃ NO ₂ G8 N CH 2-34 3,5-Cl ₂ CF ₃ CN G1 N CH 2-35 3,5-Cl ₂ CF ₃ CN G2 N CH 2-36 3,5-Cl ₂ CF ₃ CN G3 N CH 2-37 3,5-Cl ₂ CF ₃ CN G4 N CH 2-38 3,5-Cl ₂ CF ₃ CN G5 N CH 2-39 3,5-Cl ₂ CF ₃ CN G6 N CH 2-40 3,5-Cl ₂ CF ₃ CN G7 N CH 2-41 3,5-Cl ₂ CF ₃ CN G8 N CH 192-193 2-42 3,5-Cl ₂ CF ₃ CN G9 N CH

(X) _m R Y G Z BUT Mp. ° C 2-43 3,5-Cl ₂ CF ₃ NO ₂ G6 N CH 2-44 3,5-Cl ₂ CF ₃ NO ₂ G8 N CH 2-45 3,5-Cl ₂ CF ₃ CH ₃ G6 N CH 2-46 3,5-Cl ₂ CF ₃ Mes G6 N CH 2-47 3,5-Cl ₂ CF ₃ Meso G6 N CH 2-48 3,5-Cl ₂ CF ₃ MeSO ₂ G6 N CH 2-49 3,5-Cl ₂ CF ₃ CF ₃ S G6 N CH 2-50 3,5-Cl ₂ CF ₃ CF ₃ S (O) G6 N CH 2-51 3,5-Cl ₂ CF ₃ CF ₃ S (O) ₂ G6 N CH 2-52 3,5-Cl ₂ CF ₃ OCH ₃ G6 N CH 2-53 3,5-Cl ₂ CF ₃ OCF ₃ G6 N CH 2-54 3,5-Cl ₂ CF ₃ IT G6 N CH 2-55 3,5-Cl ₂ CF ₃ SH G6 N CH 2-56 3,5-Cl ₂ CF ₃ NH ₂ G6 N CH 2-57 3,5-Cl ₂ CF ₃ NHCOCH ₃ G6 N CH 2-58 3,5-Cl ₂ CF ₃ MHCO ₂ CH ₃ G6 N CH 2-59 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ CCl ₃ G6 N CH 2-60 3,5-Cl ₂ CF ₃ CN G2 3-NO ₂ CH 2-61 3,5-Cl ₂ CF ₃ CN G2 3-cn CH 2-62 3,5-Cl ₂ CF ₃ CN G6 3-NO ₂ CH 2-63 3,5-Cl ₂ CF ₃ CN G6 3-cn CH 2-64 3,5-Cl ₂ CF ₃ CN G2 Cl CH 2-65 3,5-Cl ₂ CF ₃ CN G2 Br CH 2-66 3,5-Cl ₂ CF ₃ CN G2 CH ₃ CH

(X) _m R Y G Z BUT Mp. ° C 2-67 3,5-Cl ₂ CF ₃ CN G2 CF ₃ CH 2-68 3-cl CF ₃ CN G6 N CH 2-69 3-cl CF ₃ CN G8 N CH 2-70 3-CF ₃ CF ₃ CN G6 N CH 2-71 3-CF ₃ CF ₃ CN G8 N CH 2-72 3,5- (CF ₃ ) ₂ CF ₃ CN G6 N CH 2-73 3,5- (CF ₃ ) ₂ CF ₃ CN G8 N CH 2-74 3-NO ₂ CF ₃ CN G6 N CH 2-75 3-NO ₂ CF ₃ CN G8 N CH 2-76 3,4-Cl ₂ CF ₃ CN G6 N CH 2-77 3,4-Cl ₂ CF ₃ CN G8 N CH 2-78 3,5-Br ₂ CF ₃ CN G6 N CH 2-79 3,5-Br ₂ CF ₃ CN G8 N CH 2-80 3,5-Br ₂ CF ₃ Br G6 N CH 2-81 3,5-Br ₂ CF ₃ Br G8 N CH 2-82 3,4,5-Cl ₃ CF ₃ CN G6 N CH 2-83 3,4,5-Cl ₃ CF ₃ CN G8 N CH 2-84 3,4,5-Cl ₃ CF ₃ Br G6 N CH 2-85 3,4,5-Cl ₃ CF ₃ Br G8 N CH 2-86 3,5-Me ₂ -4-NO ₂ CF ₃ CN G8 N CH 2-87 3-CH ₃ CF ₃ CN G6 N CH 2-88 3-CH ₃ O CF ₃ CN G6 N CH 2-89 3-cn CF ₃ CN G6 N CH 2-90 3-CF ₃ O CF ₃ CN G6 N CH

(X) _m R Y G Z BUT Mp. ° C 2-91 3-CF ₃ O CF ₃ CN G8 N CH 2-92 3-CH ₃ S CF ₃ CN G6 N CH 2-93 3-CH ₃ S CF ₃ CN G8 N CH 2-94 3-CH ₃ S (O) CF ₃ CN G6 N CH 2-95 3-CH ₃ S (O) ₂ CF ₃ CN G6 N CH 2-96 3-CF ₃ S CF ₃ CN G6 N CH 2-97 3-CF ₃ S (O) CF ₃ CN G6 N CH 2-98 3-CF ₃ S (O) ₂ CF ₃ CN G6 N CH 2-99 3-OH CF ₃ CN G6 N CH 2-100 3-SH CF ₃ CN G6 N CH 2-101 3,5-Cl ₂ CH ₃ Br G6 N CH 2-102 3,5-Cl ₂ CH ₃ Br G8 N CH 2-103 3,5-Cl ₂ CF ₃ Br G6 N N 2-104 3,5-Cl ₂ CF ₃ Br G8 N N 2-105 3,5-Cl ₂ CF ₃ CN G6 N N 2-106 3,5-Cl ₂ CF ₃ CN G8 N N 2-107 3,5-Cl ₂ CF ₃ C = NOCH ₃ G6 N CH 2-108 3,5-Cl ₂ CF ₃ C = NOCH ₃ G8 N CH 2-109 3,5-Cl ₂ CF ₃ NHSO ₂ CH ₃ G6 N CH 2-110 3,5-Cl ₂ CF ₃ NHSO ₂ CH ₃ G8 N CH 2-111 3,5-Cl ₂ CF ₃ NHSO ₂ CF ₃ G6 N CH 2-112 3,5-Cl ₂ CF ₃ NHSO ₂ CF ₃ G8 N CH

Table 3

(X) _m R Y R ² R ³ R ⁴ R ⁵ BUT one Mp 3-1 3,5-Cl ₂ CF ₃ N N N N PINE ₃ CH one 3-2 3,5-Cl ₂ CF ₃ N N N N SOS ₂ N ₅ CH one 3-3 3,5-Cl ₂ CF ₃ Cl N N N PINE ₃ CH one 3-4 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ CH one 3-5 3,5-Cl ₂ CF ₃ Br N N N SOS ₂ N ₅ CH one 3-6 3,5-Cl ₂ CF ₃ Br N N N CO-iso-Pr CH one 3-7 3,5-Cl ₂ CF ₃ Br N N N CO-2-Pyridyl CH N 3-8 3,5-Cl ₂ CF ₃ F N N N PINE ₃ CH N 3-9 3,5-Cl ₂ CF ₃ I N N N PINE ₃ CH N 3-10 3,5-Cl ₂ CF ₃ NO ₂ N N N PINE ₃ CH N 3-11 3,5-Cl ₂ CF ₃ CH ₃ N N N PINE ₃ CH N 3-12 3,5-Cl ₂ CF ₃ Mes N N N PINE ₃ CH N 3-13 3,5-Cl ₂ CF ₃ Meso N N N PINE ₃ CH N 3-14 3,5-Cl ₂ CF ₃ MeSO ₂ N N N PINE ₃ CH N 3-15 3,5-Cl ₂ CF ₃ CF ₃ S N N N PINE ₃ CH N 3-16 3,5-Cl ₂ CF ₃ CF ₃ S (O) N N N PINE ₃ CH N 3-17 3,5-Cl ₂ CF ₃ CF ₃ S (O) ₂ N N N PINE ₃ CH N 3-18 3,5-Cl ₂ CF ₃ OCH ₃ N N N PINE ₃ CH N 3-19 3,5-Cl ₂ CF ₃ OCF ₃ N N N PINE ₃ CH N 3-20 3,5-Cl ₂ CF ₃ IT N N N PINE ₃ CH N 3-21 3,5-Cl ₂ CF ₃ SH N N N PINE ₃ CH N

(X) _m R Y R ² R ³ R ⁴ R ⁵ BUT one Mp 3-22 3,5-Cl ₂ CF ₃ NH ₂ H H H PINE ₃ CH H 3-23 3,5-Cl ₂ CF ₃ NCHOSH ₃ N H H PINE ₃ CH H 3-24 3,5-Cl ₂ CF ₃ NCO ₂ CH ₃ N H H PINE ₃ CH H 3-25 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ -CCl ₃ N H H PINE ₃ CH H 3-26 3,5-Cl ₂ CF ₃ Cl N H Me CO-2-Pyridyl CH H 3-27 3,5-Cl ₂ CF ₃ Cl N H Me PINE ₃ CH H 3-28 3,5-Cl ₂ CF ₃ Cl N H Et PINE ₃ CH H 3-29 3,5-Cl ₂ CF ₃ Cl N H Vinyl PINE ₃ CH H 3-30 3,5-Cl ₂ CF ₃ Cl N H Propargil PINE ₃ CH H 3-31 3,5-Cl ₂ CF ₃ Cl N H CH ₂ Ph PINE ₃ CH H 3-32 3,5-Cl ₂ CF ₃ Cl N H CN PINE ₃ CH H 3-33 3,5-Cl ₂ CF ₃ Cl N H CH ₂ CF ₃ PINE ₃ CH H 3-34 3,5-Cl ₂ CF ₃ Cl N H Cyclopropyl PINE ₃ CH H 3-35 3,5-Cl ₂ CF ₃ Cl N H PINE ₃ PINE ₃ CH H 3-36 3,5-Cl ₂ CF ₃ Cl N H N SOS ₂ N ₅ CH one 3-37 3,5-Cl ₂ CF ₃ Cl N H N COC ₂ F ₅ CH one 3-38 3,5-Cl ₂ CF ₃ Cl N H H COPh CH one 3-39 3,5-Cl ₂ CF ₃ Cl N H H CO-2-Pyridyl CH one 3-40 3,5-Cl ₂ CF ₃ Cl N H H CONMe ₂ CH one 3-41 3,5-Cl ₂ CF ₃ Cl N H H CO ₂ Me CH one 3-42 3,5-Cl ₂ CF ₃ Cl N H H Cosme CH one 3-43 3,5-Cl ₂ CF ₃ Cl N H Me PINE ₃ CH one 3-44 3,5-Cl ₂ CF ₃ Cl N H 2- (Pyridyl-CO) PINE ₃ CH one

(X) _m R Y R ² R ³ R ⁴ R ⁵ BUT one Mp 3-45 3,5-Br ₂ CF ₃ Cl N N N PINE ₃ CH one 3-46 3-cl CF ₃ Cl N N N PINE ₃ CH one 3-47 3-CF ₃ CF ₃ Cl N N N PINE ₃ CH one 3-48 3,5- (CF ₃ ) ₂ CF ₃ Cl N N N PINE ₃ CH one 3-49 3,4,5-Cl ₃ CF ₃ Cl N N N PINE ₃ CH one 3-50 3,5-Me ₂ -4-NO ₂ CF ₃ Cl N N N PINE ₃ CH one 3-51 3-NO ₂ CF ₃ Cl N N N PINE ₃ CH one 3-52 3,5-Cl ₂ CF ₃ Cl N N N PINE ₃ N one 3-53 3-CH ₃ CF ₃ Cl N N N PINE ₃ CH one 3-54 3-CH ₃ O CF ₃ Cl N N N PINE ₃ CH one 3-55 3-cn CF ₃ Cl N N N PINE ₃ CH one 3-56 3-CF ₃ O CF ₃ Cl N N N PINE ₃ CH one 3-57 3-CH ₃ S CF ₃ Cl N N N PINE ₃ CH one 3-58 3-CH ₃ S (O) CF ₃ Cl N N N PINE ₃ CH one 3-59 3-CH ₃ S (O) ₂ CF ₃ Cl N N N PINE ₃ CH one 3-60 3-CF ₃ S CF ₃ Cl N N N PINE ₃ CH one 3-61 3-CF ₃ S (O) CF ₃ Cl N N N PINE ₃ CH one 3-62 3-CF ₃ S (O) ₂ CF ₃ Cl N N N PINE ₃ CH one 3-63 3-OH CF ₃ Cl N N N PINE ₃ CH one 3-64 3-SH CF ₃ Cl N N N PINE ₃ CH one 3-65 3,5-Cl ₂ CF ₃ Cl CN N N PINE ₃ CH one 3-66 3,5-Cl ₂ CF ₃ Cl Me N N PINE ₃ CH one 3-67 3,5-Cl ₂ CF ₃ Cl Me Me N PINE ₃ CH one 3-68 3,5-Cl ₂ CF ₃ Cl cyclo-Pr N N PINE ₃ CH one 3-69 3,5-Cl ₂ CF ₃ Cl CF ₃ N N PINE ₃ CH one

(X) _m R Y R ² R ³ R ⁴ R ⁵ BUT one Mp 3-70 3,5-Cl ₂ CF ₃ Cl CO ₂ Me N N PINE ₃ CH one 3-71 3,5-Cl ₂ CF ₃ Cl CH = CH ₂ N N PINE ₃ CH one 3-72 3,5-Cl ₂ CF ₃ Cl CH ₂ CH ₂ N PINE ₃ CH one 3-73 3,5-Cl ₂ CF ₃ Cl CCH N PINE ₃ CH one 3-74 3,5-Cl ₂ CF ₃ Br N N N COEt CH one 3-75 3,5-Cl ₂ CF ₃ Br N N N CO-n-Pr CH one 3-76 3,5-Cl ₂ CF ₃ Br N N N CO-iso-Pr CH one 3-77 3,5-Cl ₂ CF ₃ Br N N N Co-tert-bu CH one 3-78 3,5-Cl ₂ CF ₃ Br N N N COCF ₃ CH one 3-79 3,5-Cl ₂ CF ₃ Br N N N COPh CH one 3-80 3,5-Cl ₂ CF ₃ Br N N N CO-2-Pyridyl CH one 3-81 3,5-Cl ₂ CF ₃ Br N N N CO-3-Pyridyl CH one 3-82 3,5-Cl ₂ CF ₃ Br N N N CO-4-Pyridyl CH one 3-83 3,5-Cl ₂ CF ₃ Br N N N SOS ₆ N ₄ -F-2 CH one 3-84 3,5-Cl ₂ CF ₃ Br N N N SOS ₆ N ₄ -F-3 CH one 3-85 3,5-Cl ₂ CF ₃ Br N N N SOS ₆ N ₄ -F-4 CH one 3-86 3,5-Cl ₂ CF ₃ Br N N N SOC ₆ H ₄ -Cl-2 CH one 3-87 3,5-Cl ₂ CF ₃ Br N N N SOC ₆ H ₄ -Cl-3 CH one 3-88 3,5-Cl ₂ CF ₃ Br N N N SOC ₆ H ₄ -Cl-4 CH one 3-89 3,5-Cl ₂ CF ₃ Br N N N SOS ₆ N ₄ -Br-2 CH one 3-90 3,5-Cl ₂ CF ₃ Br N N N SOS ₆ N ₄ -Me-2 CH one

(X) _m R Y R ² R ³ R ⁴ R ⁵ BUT one Mp 3-91 3,5-Cl ₂ CF ₃ Br N N N PINE = CH ₂ CH one 3-92 3,5-Cl ₂ CF ₃ Br N N N SO-Propargil CH one 3-93 3,5-Cl ₂ CF ₃ Br N N N MeSO ₂ CH one 3-94 3,5-Cl ₂ CF ₃ Br N N N CF ₃ SO ₂ CH one 3-95 3,5-Cl ₂ CF ₃ Br N N N CONHMe CH one 3-96 3,5-Cl ₂ CF ₃ Br N N N CONMe ₂ CH one 3-97 3,5-Cl ₂ CF ₃ Br N N N CO ₂ Me CH one 3-98 3,5-Cl ₂ CF ₃ Br N N N C (O) SMe CH one 3-99 3,5-Cl ₂ CF ₃ Br N N N CSMe CH one 3-100 3,5-Cl ₂ CF ₃ Br N N N CON (Me) -OMe CH one 3-101 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ CH one 3-102 3,5-Cl ₂ CF ₃ CF ₃ N N N PINE ₃ CH one 3-103 3,5-Cl ₂ CF ₃ CN N N N PINE ₃ CH one 3-104 3,5-Cl ₂ CF ₃ NH ₂ N N N PINE ₃ CH one 3-105 3,5-Cl ₂ CF ₃ NHCOCH ₃ N N N PINE ₃ CH one 3-106 3,5-Cl ₂ CF ₃ MHCOCF ₃ N N N PINE ₃ CH one 3-107 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₃ N N N PINE ₃ CH one 3-108 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ -CCl ₃ N N N PINE ₃ CH one 3-109 3,5-Cl ₂ CH ₃ NHSO ₂ CH ₃ N N N PINE ₃ CH one 3-110 3,5-Cl ₂ CH ₃ NHSO ₂ CF ₃ N N N PINE ₃ CH one 3-111 3,5-Cl ₂ CH ₃ C = NOCH ₃ N N N PINE ₃ CH one 3-112 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ CH 2 3-113 3,5-Cl ₂ CF ₃ CF ₃ N N N PINE ₃ CH one 3-114 3,5-Cl ₂ CF ₃ CF ₃ N N N COC ₂ H ₅ CH one 3-115 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ N N N CO-cyclo-Pr CH one

(X) _m R Y R ² R ³ R ⁴ R ⁵ BUT one Mp 3-116 3,4,5-Cl ₃ CF ₃ CF ₃ N N N PINE ₃ CH one 3-117 3,4,5-Cl ₃ CF ₃ CF ₃ H H H SOS ₂ N ₅ CH one 3-118 3,4,5-Cl ₃ CF ₃ CF ₃ N H H CO-cyclo-Pr CH one 3-119 3,4-Cl ₂ -5-CF ₃ CF ₃ CF ₃ H H H PINE ₃ CH one

Table 4

(X) _m R Y T ⁴ BUT Mp. ° C 4-1 3,5-Cl ₂ CF ₃ N NO ₂ CH 4-2 3,5-Cl ₂ CF ₃ N CN CH 4-3 3,5-Cl ₂ CF ₃ N NH ₂ CH 4-4 3,5-Cl ₂ CF ₃ N CO ₂ Et CH 161-163 4-5 3,5-Cl ₂ CF ₃ N CO ₂ H CH 4-6 3,5-Cl ₂ CF ₃ NO ₂ CO ₂ Me CH 4-7 3,5-Cl ₂ CF ₃ NO ₂ CO ₂ H CH 4-8 3,5-Cl ₂ CF ₃ NH ₂ CO ₂ Me CH 4-9 3,5-Cl ₂ CF ₃ F CO ₂ Me CH 4-10 3,5-Cl ₂ CF ₃ Cl CO ₂ Me CH 4-11 3,5-Cl ₂ CF ₃ Cl CO ₂ -tret-Bu CH 4-12 3,5-Cl ₂ CF ₃ Cl CO ₂ H CH 4-13 3,5-Cl ₂ CF ₃ Br CO ₂ Me CH

(X) _m R Y T ⁴ BUT Mp. ° C 4-14 3,5-Cl ₂ CF ₃ I CO ₂ Me CH 4-15 3,5-Cl ₂ CF ₃ CH ₃ CO ₂ Me CH 4-16 3,5-Cl ₂ CF ₃ Cl CH ₃ CH 4-17 3,5-Cl ₂ CF ₃ CN F CH 184-186 4-18 3,5-Cl ₂ CF ₃ CH ₃ NO ₂ CH 4-19 3,5-Cl ₂ CF ₃ CH ₃ NO ₂ CH 4-20 3,5-Cl ₂ CF ₃ Br NO ₂ CH 4-21 3,5-Cl ₂ CF ₃ Br NH ₂ CH 4-22 3-CF ₃ CF ₃ NO ₂ CO ₂ Me CH 146-148 4-23 3-CF ₃ CF ₃ NO ₂ CO ₂ H CH 4-24 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CO ₂ Me CH 4-25 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CO ₂ H CH 4-26 3,4-Cl ₂ CF ₃ NO ₂ CO ₂ Me CH 4-27 3,4-Cl ₂ CF ₃ NO ₂ CO ₂ Me CH 4-28 3-cl CF ₃ NO ₂ CO ₂ Me CH 142-144 4-29 3-cl CF ₃ NO ₂ CO ₂ Me CH 4-30 3,5-Br ₂ CF ₃ NO ₂ CO ₂ Me CH 4-31 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ Me CH 4-32 3,5-Me ₂ -4-NO ₂ CF ₃ NO ₂ CO ₂ Me CH 4-33 3-NO ₂ CF ₃ NO ₂ CO ₂ Me CH 4-34 3-CH ₃ CF ₃ NO ₂ CO ₂ Me CH 4-35 3-CH ₃ O CF ₃ NO ₂ CO ₂ Me CH 4-36 3-cn CF ₃ NO ₂ CO ₂ Me CH 4-37 3-CF ₃ O CF ₃ NO ₂ CO ₂ Me CH 4-38 3-CH ₃ S CF ₃ NO ₂ CO ₂ Me CH

(X) _m R Y T ⁴ BUT Mp. ° C 4-39 3-CH ₃ S (O) CF ₃ NO ₂ CO ₂ Me CH 4-40 3-CH ₃ S (O) ₂ CF ₃ NO ₂ CO ₂ Me CH 4-41 3-CF ₃ S CF ₃ NO ₂ CO ₂ Me CH 4-42 3-CF ₃ S (O) CF ₃ NO ₂ CO ₂ Me CH 4-43 3-CF ₃ S (O) ₂ CF ₃ NO ₂ CO ₂ Me CH 4-44 3-OH CF ₃ NO ₂ CO ₂ Me CH 4-45 3-SH CF ₃ NO ₂ CO ₂ Me CH 4-46 3,5-Cl ₂ CF ₃ H CO ₂ Me N 4-47 3-NO ₂ CF ₃ NO ₂ CO ₂ Me CH 4-48 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ Me CH 4-49 2-cl CF ₃ NO ₂ CO ₂ Me CH 4-50 2-cl CF ₃ NO ₂ CO ₂ H CH 4-51 4-cl CF ₃ NO ₂ CO ₂ Me CH 4-52 4-cl CF ₃ NO ₂ CO ₂ H CH 4-53 3,5-Cl ₂ CF ₃ NO ₂ CO ₂ Et CH 4-54 3,5-Cl ₂ CF ₃ CF ₃ CO ₂ H CH 4-55 3,5-Me ₂ -4-NO ₂ CF ₃ NO ₂ CO ₂ H CH 4-56 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ Me CH 4-57 3,5-Cl ₂ CF ₃ CN CO ₂ H CH 4-58 3,5-Cl ₂ CF ₃ CN CO ₂ Me CH 4-59 3,5-Cl ₂ CF ₃ H CO ₂ -tret-Bu N 4-60 3,5-Cl ₂ CF ₃ H CO ₂ H N 4-61 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ CO ₂ Et CH 4-62 3,5-Cl ₂ CF ₃ CF ₃ F CH 4-63 3,5-Cl ₂ CF ₃ CF ₃ NO ₂ CH 4-64 3,5-Cl ₂ CF ₃ CF ₃ NH ₂ CH

(X) _m R Y T ⁴ BUT Mp. ° C 4-65 3,5-Cl ₂ CF ₃ F CO ₂ Et CH 4-66 3,4,5-Cl ₃ CF ₃ CF ₃ CO ₂ Et CH 4-67 3,4,5-Cl ₃ CF ₃ CF ₃ CO ₂ H CH

Table 5

(X) m R T ¹ Mp. ° C 5-1 2-cl CF ₃ CH ₂ Ph 5-2 2-cl CF ₃ N 5-3 3-cl CF ₃ CH ₂ Ph 5-4 3-cl CF ₃ N 5-5 4-cl CF ₃ CH ₂ Ph 5-6 4-cl CF ₃ N 5-7 2,3-Cl ₂ CF ₃ CH ₂ Ph 5-8 2,3-Cl ₂ CF ₃ N 5-9 3,4-Cl ₂ CF ₃ CH ₂ Ph 5-10 3,4-Cl ₂ CF ₃ N 5-11 3,5-Cl ₂ CF ₃ CH ₂ Ph 5-12 3,5-Cl ₂ CF ₃ N 5-13 3,5-Cl ₂ CF ₃ H, salt with HCl 5-14 3,4,5-Cl ₃ CF ₃ CH ₂ Ph 5-15 3,4,5-Cl ₃ CF ₃ N 5-16 3-CF ₃ CF ₃ CH ₂ Ph 5-17 3-CF ₃ CF ₃ N 5-18 3,5- (CF ₃ ) ₂ CF ₃ CH ₂ Ph 5-19 3,5- (CF ₃ ) ₂ CF ₃ N 5-20 3-br CF ₃ CH ₂ Ph 5-21 3-br CF ₃ N

(X) _m R T ¹ Mp. ° C 5-22 3,5-Br ₂ CF ₃ CH ₂ Ph 5-23 3,5-Br ₂ CF ₃ N 5-24 3-NO ₂ CF ₃ CH ₂ Ph 5-25 3-NO ₂ CF ₃ N 5-26 3,5-Me ₂ -4-NO ₂ CF ₃ CH ₂ Ph 5-27 3,5-Me ₂ -4-NO ₂ CF ₃ N 5-28 3-cn CF ₃ CH ₂ Ph 5-29 3-cn CF ₃ N 5-30 3-OCF ₃ CF ₃ CH ₂ Ph 5-31 3-OCF ₃ CF ₃ N 5-32 3-SCF ₃ CF ₃ CH ₂ Ph 5-33 3-SCF ₃ CF ₃ N 5-34 3-S (O) CF ₃ CF ₃ CH ₂ Ph 5-35 3-S (O) CF ₃ CF ₃ N 5-36 3-S (O) ₂ CF ₃ CF ₃ CH ₂ Ph 5-37 3-S (O) ₂ CF ₃ CF ₃ N 5-38 3,4-Cl ₂ -5-CF ₃ CF ₃ CH ₂ Ph 5-39 3,4-Cl ₂ -5-CF ₃ CF ₃ N

Table 6

T ² T ³ Mp. ° C 6-1 CH ₃ CH ₃ 6-2 CH ₃ CH ₂ CH ₃ 6-3 CH ₂ CH ₃ CH ₂ CH ₃ 6-4 n-Pr n-Pr 6-5 iso-Pr iso-Pr 6-6 cyclo-Pr cyclo-Pr

T ² T ³ Mp. ° C 6-7 n-bu n-bu 6-8 tert-bu tert-bu 6-9 n-pen n-pen

Table 7

(X) _m R Y R ¹ R ² W Mp. ° C 7-1 3,5-Cl ₂ CF ₃ N CF ₃ CH ₂ N O 7-2 3,5-Cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-3 3,5-Cl ₂ CF ₃ CH ₃ CF ₃ CH ₂ N O 7-4 3,5-Cl ₂ CF ₃ CH ₃ 2-Pyridyl-CH ₂ N O 7-5 3,5-Cl ₂ CF ₃ F CF ₃ CH ₂ N O 7-6 3,5-Cl ₂ CF ₃ F 2-Pyridyl-CH ₂ N O 7-7 3,5-Cl ₂ CF ₃ Cl CF ₃ CH ₂ N O 7-8 3,5-Cl ₂ CF ₃ Cl 2-Pyridyl-CH ₂ N O 7-9 3,5-Cl ₂ CF ₃ Br CF ₃ CH ₂ N O 7-10 3,5-Cl ₂ CF ₃ Br 2-Pyridyl-CH ₂ N O 7-11 3,5-Cl ₂ CF ₃ Br cyclo-Pr N O 7-12 3,5-Cl ₂ CF ₃ Br NCCH ₂ CH ₂ N O 7-13 3,5-Cl ₂ CF ₃ I CF ₃ CH ₂ N O 7-14 3,5-Cl ₂ CF ₃ I 2-Pyridyl-CH ₂ N O 7-15 3,5-Cl ₂ CF ₃ NO ₂ CF ₃ CH ₂ N O 7-16 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O

(X) _m R Y R ¹ R ² W Mp. ° C 7-17 3-cl CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-18 3-cl CF ₃ NO ₂ CF ₃ CH ₂ N O 7-19 3-br CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-20 3-CF ₃ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-21 3-CF ₃ CF ₃ NO ₂ CF ₃ CH ₂ N O 7-22 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-23 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CF ₃ CH ₂ N O 7-24 3-NO ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-25 3,5-Cl ₂ CF ₃ CF ₃ 2-Pyridyl-CH ₂ N O 7-26 3,5-Cl ₂ CF ₃ CF ₃ CF ₃ CH ₂ N O 7-27 3,5-Cl ₂ CF ₃ CH ₃ O 2-Pyridyl-CH ₂ N O 7-28 3,5-Cl ₂ CF ₃ CN 2-Pyridyl-CH ₂ N O 7-29 3,5-Cl ₂ CF ₃ CF ₃ O 2-Pyridyl-CH ₂ N O 7-30 3,5-Cl ₂ CF ₃ CH ₃ S 2-Pyridyl-CH ₂ N O 7-31 3,5-Cl ₂ CF ₃ CH ₃ S (O) 2-Pyridyl-CH ₂ N O 7-32 3,5-Cl ₂ CF ₃ CH ₃ S (O) ₂ 2-Pyridyl-CH ₂ N O 7-33 3,5-Cl ₂ CF ₃ CF ₃ S 2-Pyridyl-CH ₂ N O 7-34 3,5-Cl ₂ CF ₃ CF ₃ S (O) 2-Pyridyl-CH ₂ N O 7-35 3,5-Cl ₂ CF ₃ CF ₃ S (O) ₂ 2-Pyridyl-CH ₂ N O 7-36 3,5-Cl ₂ CF ₃ IT 2-Pyridyl-CH ₂ N O 7-37 3,5-Cl ₂ CF ₃ SH 2-Pyridyl-CH ₂ N O 7-38 3,5-Cl ₂ CF ₃ NH ₂ 2-Pyridyl-CH ₂ N O 7-39 3,5-Cl ₂ CF ₃ NHCOCH ₃ 2-Pyridyl-CH ₂ N O 7-40 3,5-Cl ₂ CF ₃ NHCOCF ₃ 2-Pyridyl-CH ₂ N O 7-41 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₃ 2-Pyridyl-CH ₂ N O 7-42 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ CCl ₃ 2-Pyridyl-CH ₂ N O

(X) _m R Y R ¹ R ² W Mp. ° C 7-43 3-CH ₃ CF ₃ N 2-Pyridyl-CH ₂ N O 7-44 3-CH ₃ O CF ₃ N 2-Pyridyl-CH ₂ N O 7-45 3-cn CF ₃ N 2-Pyridyl-CH ₂ N O 7-46 3-CF ₃ O CF ₃ N 2-Pyridyl-CH ₂ N O 7-47 3-CH ₃ S CF ₃ N 2-Pyridyl-CH ₂ N O 7-48 3-CH ₃ S (O) CF ₃ N 2-Pyridyl-CH ₂ N O 7-49 3-CH ₃ S (O) ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-50 3-CF ₃ S CF ₃ N 2-Pyridyl-CH ₂ N O 7-51 3-CF ₃ S (O) CF ₃ N 2-Pyridyl-CH ₂ N O 7-52 3-CF ₃ S (O) ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-53 3-OH CF ₃ N 2-Pyridyl-CH ₂ N O 7-54 3-SH CF ₃ N 2-Pyridyl-CH ₂ N O 7-55 3,4-Cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-56 3,4-Cl ₂ CF ₃ N CF ₃ CH ₂ N O 7-57 3,4,5-Cl ₃ CF ₃ N 2-Pyridyl-CH ₂ N O 7-58 3,4,5-Cl ₃ CF ₃ N CF ₃ CH ₂ N O 7-59 3,5-Br ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-60 3,5-Br ₂ CF ₃ N CF ₃ CH ₂ N O 7-61 3,5-Me ₂ -4-NO ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-62 3,5-Me ₂ -4-NO ₂ CF ₃ N CF ₃ CH ₂ N O 7-63 3,5-Cl ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 7-64 3,5-Cl ₂ CF ₃ NO ₂ N N O 7-65 3,5-Cl ₂ CF ₃ NO ₂ Me N O 7-66 3,5-Cl ₂ CF ₃ NO ₂ iso-Pr N O 7-67 3,5-Cl ₂ CF ₃ NO ₂ Phch ₂ N O 7-68 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ CO ₂ CH ₃ N O

(X) _m R Y R ¹ R ² W Mp. ° C 7-69 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ CONMe N O 7-70 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ -cyclo-Pr N O 7-71 3,5-Cl ₂ CF ₃ NO ₂ SO ₂ Me N O 7-72 3,5-Cl ₂ CF ₃ NO ₂ SO ₂ CF ₃ N O 7-73 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ = CHCH ₂ N O 7-74 3,5-Cl ₂ CF ₃ NO ₂ HC≡CCH ₂ N O 7-75 3,5-Cl ₂ CF ₃ NO ₂ CH ₂ CN N O 7-76 3,5-Cl ₂ CF ₃ NO ₂ C (Me) ₂ CH ₂ SCH ₃ N O 7-77 3,5-Cl ₂ CF ₃ NO ₂ 2-F-C ₆ H ₄ N O 7-78 3,5-Cl ₂ CH ₃ H 2-Pyridyl-CH ₂ N O 7-79 3,5-Cl ₂ CF ₃ H 2-Pyridyl-CH ₂ CH ₃ O 7-80 3-NO ₂ CF ₃ NO ₂ CF ₃ CH ₂ N O 7-81 3,5-Cl ₂ CF ₃ Cl 2-Pyridyl-CH ₂ N S 7-82 2-cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-83 2,3-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-84 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-85 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-86 3,5-Cl ₂ CF ₃ NO ₂ 2- (6-Cl-Pyridyl) -CH ₂ N O 7-87 3,5-Cl ₂ CF ₃ NO ₂ 2- (6-Cl-Pyridyl) -CH ₂ N O 7-88 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyrinidinyl-CH ₂ N O 7-89 3,5-Cl ₂ CF ₃ NO ₂ 1- (1-Ethylpyrrolidin-2-yl) -CH ₂ N O 7-90 3,5-Cl ₂ CF ₃ CF ₃ CF ₃ CH ₂ N O 7-91 3,5-Cl ₂ CF ₃ CF ₃ 2- (6-Cl-Pyridyl) -CH ₂ N O 7-92 3,5-Cl ₂ CF ₃ NO ₂ Me ₂ NCH = O

(X) _m R Y R ¹ R ² W Mp. ° C 7-93 3,5-Cl ₂ CF ₃ NO ₂ EtON = CH N O 7-94 3,5-Cl ₂ CF ₃ C = NOCH ₃ 2-Pyridyl-CH ₂ 7-95 4-cl CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 7-96 4-cl CF ₃ NO ₂ CF ₃ CH ₂ N O 7-97 3,5-Cl ₂ CF ₃ CN CF ₃ CH ₂ N O 7-98 3,5-Cl ₂ CF ₃ CF ₃ N N O 7-99 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ 2-Pyridyl-CH ₂ N O 7-100 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ CF ₃ CH ₂ N O

Table 8

(X) _m R Y R ¹ R ² W Mp. ° C 8-1 3,5-Cl ₂ CF ₃ CH ₃ CF ₃ CH ₂ N O 8-2 3,5-Cl ₂ CF ₃ CH ₃ 2-Pyridyl-CH ₂ N O 8-3 3,5-Cl ₂ CF ₃ F CF ₃ CH ₂ N O 8-4 3,5-Cl ₂ CF ₃ F 2-Pyridyl-CH ₂ N O 8-5 3,5-Cl ₂ CF ₃ Cl CF ₃ CH ₂ N O 8-6 3,5-Cl ₂ CF ₃ Cl 2-Pyridyl-CH ₂ N O 8-7 3,5-Cl ₂ CF ₃ Br CF ₃ CH ₂ N O 8-8 3,5-Cl ₂ CF ₃ Br 2-Pyridyl-CH ₂ N O 8-9 3,5-Cl ₂ CF ₃ Br cyclo-Pr N O 8-10 3,5-Cl ₂ CF ₃ Br NCCH ₂ CH ₂ N O

(X) _m R Y R ¹ R ² W Mp. ° C 8-11 3,5-Cl ₂ CF ₃ I CF ₃ CH ₂ N O 8-12 3,5-Cl ₂ CF ₃ I 2-Pyridyl-CH ₂ N O 8-13 3,5-Cl ₂ CF ₃ NO ₂ CF ₃ CH ₂ N O 8-14 3,5-Cl ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 8-15 3-cl CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 8-16 3-cl CF ₃ NO ₂ CF ₃ CH ₂ N O 8-17 3-br CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 8-18 3-CF ₃ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 8-19 3-CF ₃ CF ₃ NO ₂ CF ₃ CH ₂ N O 8-20 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 8-21 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CF ₃ CH ₂ N O 8-22 3-NO ₂ CF ₃ NO ₂ 2-Pyridyl-CH ₂ N O 8-23 3,5-Cl ₂ CF ₃ CF ₃ 2-Pyridyl-CH ₂ N O 8-24 3,5-Cl ₂ CF ₃ CF ₃ CF ₃ CH ₂ N O 8-25 3,5-Cl ₂ CF ₃ CF ₃ N N O 8-26 3,5-Cl ₂ CF ₃ CH ₃ O 2-Pyridyl-CH ₂ N O 8-27 3,5-Cl ₂ CF ₃ CN 2-Pyridyl-CH ₂ N O 8-28 3,5-Cl ₂ CF ₃ CF ₃ O 2-Pyridyl-CH ₂ N O 8-29 3,5-Cl ₂ CF ₃ CH ₃ S 2-Pyridyl-CH ₂ N O 8-30 3,5-Cl ₂ CF ₃ CH ₃ S (O) 2-Pyridyl-CH ₂ N O 8-31 3,5-Cl ₂ CF ₃ CH ₃ S (O) ₂ 2-Pyridyl-CH ₂ N O 8-32 3,5-Cl ₂ CF ₃ CF ₃ S 2-Pyridyl-CH ₂ N O 8-33 3,5-Cl ₂ CF ₃ CF ₃ S (O) 2-Pyridyl-CH ₂ N O 8-34 3,5-Cl ₂ CF ₃ CF ₃ S (O) ₂ 2-Pyridyl-CH ₂ N O 8-35 3,5-Cl ₂ CF ₃ IT 2-Pyridyl-CH ₂ N O

(X) _m R Y R ¹ R ² W Mp. ° C 8-36 3,5-Cl ₂ CF ₃ SH 2-Pyridyl-CH ₂ N O 8-37 3,5-Cl ₂ CF ₃ NH ₂ 2-Pyridyl-CH ₂ N O 8-38 3,5-Cl ₂ CF ₃ NHCOCH ₃ 2-Pyridyl-CH ₂ N O 8-39 3,5-Cl ₂ CF ₃ NHCOCF ₃ 2-Pyridyl-CH ₂ N O 8-40 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₃ 2-Pyridyl-CH ₂ N O 8-41 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ CCl ₃ 2-Pyridyl-CH ₂ N O 8-42 3-CH ₃ CF ₃ N 2-Pyridyl-CH ₂ N O 8-43 3-CH ₃ O CF ₃ N 2-Pyridyl-CH ₂ N O 8-44 3-cn CF ₃ N 2-Pyridyl-CH ₂ N O 8-45 3-CF ₃ O CF ₃ N 2-Pyridyl-CH ₂ N O 8-46 3-CH ₃ S CF ₃ N 2-Pyridyl-CH ₂ N O 8-47 3-CH ₃ S (P) CF ₃ N 2-Pyridyl-CH ₂ N O 8-48 3-CH ₃ S (O) ₂ CF ₃ N 2-Pyridyl-CH ₂ N O 8-49 3-CF ₃ S CF ₃ N 2-Pyridyl-CH ₂ N O

Table 9

(X) _m R Y R ² R ³ R ⁴ R ⁵ one Mp 9-1 3,5-Cl ₂ CF ₃ N N N N PINE ₃ one 9-2 3,5-Cl ₂ CF ₃ N N N N COC ₂ H ₅ one 9-3 3,5-Cl ₂ CF ₃ Cl N N N PINE ₃ one

(X) _m R Y R ² R ³ R ⁴ R ⁵ one Mp 9-4 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ one 9-5 3,5-Cl ₂ CF ₃ Br N N N COC ₂ H ₅ one 9-6 3,5-Cl ₂ CF ₃ Br N N N CO-iso-Pr one 9-7 3,5-Cl ₂ CF ₃ Br N N N CO-2-Pyridyl one 9-8 3,5-Cl ₂ CF ₃ F N N N PINE ₃ one 9-9 3,5-Cl ₂ CF ₃ I N N N PINE ₃ one 9-10 3,5-Cl ₂ CF ₃ NO ₂ N N N PINE ₃ one 9-11 3,5-Cl ₂ CF ₃ CH3 N N N PINE ₃ one 9-12 3,5-Cl ₂ CF ₃ Mes N N N PINE ₃ one 9-13 3,5-Cl ₂ CF ₃ Meso N N N PINE ₃ one 9-14 3,5-Cl ₂ CF ₃ MeSO ₂ N N N PINE ₃ one 9-15 3,5-Cl ₂ CF ₃ CF ₃ S N N N PINE ₃ one 9-16 3,5-Cl ₂ CF ₃ CF ₃ S (O) N N N PINE ₃ one 9-17 3,5-Cl ₂ CF ₃ CF ₃ S (O) ₂ N N N PINE ₃ one 9-18 3,5-Cl ₂ CF ₃ OCH ₃ N N N PINE ₃ one 9-19 3,5-Cl ₂ CF ₃ OCF ₃ N N N PINE ₃ one 9-20 3,5-Cl ₂ CF ₃ IT N N N PINE ₃ one 9-21 3,5-Cl ₂ CF ₃ SH N N N PINE ₃ one 9-22 3,5-Cl ₂ CF ₃ NH ₂ N N N PINE ₃ one 9-23 3,5-Cl ₂ CF ₃ NHCOCH ₃ N N N PINE ₃ one 9-24 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₃ N N N PINE ₃ one 9-25 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ -CCl ₃ N N N PINE ₃ one 9-26 3,5-Cl ₂ CF ₃ Cl N N Me CO-2-Pyridyl one 9-27 3,5-Cl ₂ CF ₃ Cl N N Me PINE ₃ one 9-28 3,5-Cl ₂ CF ₃ Cl N N Et PINE ₃ one

(X) _m R Y R ² R ³ R ⁴ R ⁵ one Mp 9-29 3,5-Cl ₂ CF ₃ Cl H H Vinyl PINE ₃ one 9-30 3,5-Cl ₂ CF ₃ Cl H H Propargil PINE ₃ one 9-31 3,5-Cl ₂ CF ₃ Cl H H CH ₂ Ph PINE ₃ one 9-32 3,5-Cl ₂ CF ₃ Cl H H CN PINE ₃ one 9-33 3,5-Cl ₂ CF ₃ Cl H H CH ₂ CF ₃ PINE ₃ one 9-34 3,5-Cl ₂ CF ₃ Cl H H cyclo-Pr PINE ₃ one 9-35 3,5-Cl ₂ CF ₃ Cl H H PINE ₃ PINE ₃ one 9-36 3,5-Cl ₂ CF ₃ Cl H H N SOS ₂ N ₅ one 9-37 3,5-Cl ₂ CF ₃ Cl H H N COC ₂ F ₅ one 9-38 3,5-Cl ₂ CF ₃ Cl H H N COPh one 9-39 3,5-Cl ₂ CF ₃ Cl H H N CO-2-Pyridyl one 9-40 3,5-Cl ₂ CF ₃ Cl H H N CONMe ₂ one 9-41 3,5-Cl ₂ CF ₃ Cl H H N CO ₂ Me one 9-42 3,5-Cl ₂ CF ₃ Cl H H N Cosme one 9-43 3,5-Cl ₂ CF ₃ Cl H H Me PINE ₃ one 9-44 3,5-Cl ₂ CF ₃ Cl H H 2-Pyridyl-CO PINE ₃ one 9-45 3,5-Br ₂ SR Cl H H N PINE ₃ one 9-46 3-cl CF ₃ Cl H H N PINE ₃ one 9-47 3-CF ₃ CF ₃ Cl H H N PINE ₃ one 9-48 3,5- (CF ₃ ) ₂ CF ₃ Cl H H N PINE ₃ one 9-49 3,4,5-Cl ₃ CF ₃ Cl H H N PINE ₃ one 9-50 3,5-Me ₂ -4-NO ₂ CF ₃ Cl H H N PINE ₃ one 9-51 3-NO ₂ CF ₃ Cl H H N PINE ₃ one 9-52 3-CH ₃ CF ₃ Cl H H N PINE ₃ one

(X) _m R Y R ² R ³ R ⁴ R ⁵ one Mp 9-53 3-CH ₃ O CF ₃ Cl H H H PINE ₃ one 9-54 3-cn CF ₃ Cl H H H PINE ₃ one 9-55 3-CF ₃ O CF ₃ Cl H H H PINE ₃ one 9-56 3-CH ₃ S CF ₃ Cl H H H PINE ₃ one 9-57 3-CH ₃ S (O) CF ₃ Cl H H H PINE ₃ one 9-58 3-CH ₃ S (O) ₂ CF ₃ Cl H H H PINE ₃ one 9-59 3-CF ₃ S CF ₃ Cl H H H PINE ₃ one 9-60 3-CF ₃ S (O) CF ₃ Cl H H H PINE ₃ one 9-61 3-CF ₃ S (O) ₂ CF ₃ Cl H H H PINE ₃ one 9-62 3-OH CF ₃ Cl H H H PINE ₃ one 9-63 3-SH CF ₃ Cl H H H PINE ₃ one 9-64 3,5-Cl ₂ CF ₃ Cl CN H H PINE ₃ one 9-65 3,5-Cl ₂ CF ₃ Cl Me H H PINE ₃ one 9-66 3,5-Cl ₂ CF ₃ Cl Me Me H PINE ₃ one 9-67 3,5-Cl ₂ CF ₃ Cl cyclo-Pr N H PINE ₃ one 9-68 3,5-Cl ₂ CF ₃ Cl CF ₃ H H PINE ₃ one 9-69 3,5-Cl ₂ CF ₃ Cl CO ₂ Me H H PINE ₃ one 9-70 3,5-Cl ₂ CF ₃ Cl CH = CH ₂ H H PINE ₃ one 9-71 3,5-Cl ₂ CF ₃ Cl CH ₂ CH ₂ H H PINE ₃ one 9-72 3,5-Cl ₂ CF ₃ Cl Cch H H PINE ₃ one 9-73 3,5-Cl ₂ CF ₃ Br H H H COEt one 9-74 3,5-Cl ₂ CF ₃ Br H H H CO-n-Pr one 9-75 3,5-Cl ₂ CF ₃ Br H H H CO-iso-Pr one 9-76 3,5-Cl ₂ CF ₃ Br H H H Co-tert-bu one 9-77 3,5-Cl ₂ CF ₃ Br H H H COCF ₃ one 9-78 3,5-Cl ₂ CF ₃ Br H H H COPh one

(X) _m R Y R ² R ³ R ⁴ R ⁵ one Mp 9-79 3,5-Cl ₂ CF ₃ Br N N N SO-Pyridyl-2 one 9-80 3,5-Cl ₂ CF ₃ Br N N N SO-Pyridyl-3 one 9-81 3,5-Cl ₂ CF ₃ Br N N N CO-Pyridyl-CO-4 one 9-82 3,5-Cl ₂ CF ₃ Br N N N 2-F-C ₆ H ₄ -CO one 9-83 3,5-Cl ₂ CF ₃ Br N N N 3-F-C ₆ H ₄ -CO one 9-84 3,5-Cl ₂ CF ₃ Br N N N 4-F-C ₆ H ₄ -CO one 9-85 3,5-Cl ₂ CF ₃ Br N N N 2-Cl-C ₆ H ₄ -CO one 9-86 3,5-Cl ₂ CF ₃ Br N N N 3-Cl-C ₆ H ₄ -CO one 9-87 3,5-Cl ₂ CF ₃ Br N N N 4-Cl-C ₆ H ₄ -CO one 9-88 3,5-Cl ₂ CF ₃ Br N N N 2-Br-C ₆ H ₄ -CO one 9-89 3,5-Cl ₂ CF ₃ Br N N N 2-Me-C ₆ H ₄ -CO one 9-90 3,5-Cl ₂ CF ₃ Br N N N SO-Vinyl one 9-91 3,5-Cl ₂ CF ₃ Br N N N SO-Propargil one 9-92 3,5-Cl ₂ CF ₃ Br N N N MeSO ₂ one 9-93 3,5-Cl ₂ CF ₃ Br N N N CF ₃ SO ₂ one 9-94 3,5-Cl ₂ CF ₃ Br N N N CONHMe one 9-95 3,5-Cl ₂ CF ₃ Br N N N CONMe ₂ one 9-96 3,5-Cl ₂ CF ₃ Br N N N CO ₂ Me one 9-97 3,5-Cl ₂ CF ₃ Br N N N C (O) SMe one 9-98 3,5-Cl ₂ CF ₃ Br N N N CSMe one 9-99 3,5-Cl ₂ CF ₃ Br N N N CON (Me) OMe one 9-100 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ one 9-101 3,5-Cl ₂ CH ₃ CF ₃ N N N PINE ₃ one 9-102 3,5-Cl ₂ CH ₃ CN N N N PINE ₃ one 9-103 3,5-Cl ₂ CH ₃ NH ₂ N N N PINE ₃ one

(X) _m R At R ² R ³ R ⁴ R ⁵ one Mp 9-104 3,5-Cl ₂ CH ₃ NCHOSH ₃ N N N PINE ₃ one 9-105 3,5-Cl ₂ CH ₃ NHCOCF ₃ N N N PINE ₃ one 9-106 3,5-Cl ₂ CH ₃ HHCO ₂ CH ₃ N N N PINE ₃ one 9-107 3,5-Cl ₂ CH ₃ NHCO ₂ CH ₂ -CCl ₃ N N N PINE ₃ one 9-108 3,5-Cl ₂ CH ₃ NHSO ₂ CH ₃ N N N PINE ₃ one 9-109 3,5-Cl ₂ CH ₃ NHSO ₂ CF ₃ N N N PINE ₃ one 9-110 3,5-Cl ₂ CH ₃ C = NOSH ₃ N N N PINE ₃ one 9-111 3,5-Cl ₂ CH ₃ Br N N N PINE ₃ 2 9-112 3,5- (CF ₃ ) ₂ CH ₃ CF ₃ N N N PINE ₃ one 9-113 3,5- (CF ₃ ) ₂ CH ₃ CF ₃ N N N SOS ₂ N ₅ one 9-114 3,5- (CF ₃ ) ₂ CH ₃ CF ₃ N N N CO-cyclo-Pr one 9-115 3,4,5-Cl ₃ CF ₃ CF ₃ N N N PINE ₃ one 9-116 3,4,5-Cl ₃ CF ₃ CF ₃ N N N COC ₂ H ₅ one 9-117 3,4,5-Cl ₃ CF ₃ CF ₃ N N N CO-cyclo-Pr one 9-118 3,4-Cl ₂ -5-CF ₃ CF ₃ CF ₃ N N N PINE ₃ one

Table 10

(X) m R Y R ² R ³ R ⁴ R ⁵ one Mp 10-1 3,5-Cl ₂ CF ₃ Cl N N N PINE ₃ one 10-2 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ one 10-3 3,5-Cl ₂ CF ₃ Br N N N SOS ₂ N ₅ one 10-4 3,5-Cl ₂ CF ₃ Br N N N CO-iso-Pr one 10-5 3,5-Cl ₂ CF ₃ Br N N N CO-2-Pyridyl one 10-6 3,5-Cl ₂ CF ₃ F N N N PINE ₃ one 10-7 3,5-Cl ₂ CF ₃ I N N N PINE ₃ one 10-8 3,5-Cl ₂ CF ₃ NO ₂ N N N PINE ₃ one 10-9 3,5-Cl ₂ CF ₃ CH ₃ N N N PINE ₃ one 10-10 3,5-Cl ₂ CF ₃ Mes N N N PINE ₃ one 10-11 3,5-Cl ₂ CF ₃ Meso N N N PINE ₃ one 10-12 3,5-Cl ₂ CF ₃ MeSO ₂ N N N PINE ₃ one 10-13 3,5-Cl ₂ CF ₃ CF ₃ S N N N PINE ₃ one 10-14 3,5-Cl ₂ CF ₃ CF ₃ S (O) N N N PINE ₃ one 10-15 3,5-Cl ₂ CF ₃ CF ₃ S (O) ₂ N N N PINE ₃ one 10-16 3,5-Cl ₂ CF ₃ OCH ₃ N N N PINE ₃ one 10-17 3,5-Cl ₂ CF ₃ OCF ₃ N N N PINE ₃ one 10-18 3,5-Cl ₂ CF ₃ IT N N N PINE ₃ one 10-19 3,5-Cl ₂ CF ₃ SH N N N PINE ₃ one 10-20 3,5-Cl ₂ CF ₃ NH ₂ N N N PINE ₃ one

(X) m R Y R ² R ³ R ⁴ R ⁵ one Mp 10-21 3,5-Cl ₂ CF ₃ NCHOSH ₃ H H H PINE ₃ one 10-22 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₃ H H H PINE ₃ one 10-23 3,5-Cl ₂ CF ₃ NHCO ₂ CH ₂ -CCl ₃ H H H PINE ₃ one 10-24 3,5-Cl ₂ CF ₃ Cl H H Me CO-2-Pyridyl one 10-25 3,5-Cl ₂ CF ₃ Cl H H Me PINE ₃ one 10-26 3,5-Cl ₂ CF ₃ Cl H H Et PINE ₃ one 10-27 3,5-Cl ₂ CF ₃ Cl H H Vinyl PINE ₃ one 10-28 3,5-Cl ₂ CF ₃ Cl H H Propargil PINE ₃ one 10-29 3,5-Cl ₂ CF ₃ Cl H H CH ₂ Ph PINE ₃ one 10-30 3,5-Cl ₂ CF ₃ Cl H H CN PINE ₃ one 10-31 3,5-Cl ₂ CF ₃ Cl H H CH ₂ CF ₃ PINE ₃ one 10-32 3,5-Cl ₂ CF ₃ Cl H H Cycle Pr PINE ₃ one 10-33 3,5-Cl ₂ CF ₃ Cl H H PINE ₃ PINE ₃ one 10-34 3,5-Cl ₂ CF ₃ Cl H H N SOS ₂ N ₅ one 10-35 3,5-Cl ₂ CF ₃ Cl H H N COC ₂ F ₅ one 10-36 3,5-Cl ₂ CF ₃ Cl H H H COPh one 10-37 3,5-Cl ₂ CF ₃ Cl H H H CO-2-Pyridyl one 10-38 3,5-Cl ₂ CF ₃ Cl H H H CONMe ₂ one 10-39 3,5-Cl ₂ CF ₃ Cl H H H CO ₂ Me one 10-40 3,5-Cl ₂ CF ₃ Cl H H H Cosme one 10-41 3,5-Cl ₂ CF ₃ Cl H H Me PINE ₃ one 10-42 3,5-Cl ₂ CF ₃ Cl H H 2-Pyridyl-CO PINE ₃ one 10-43 3,5-Br ₂ CF ₃ Cl H H N PINE ₃ one

(X) m R Y R ² R ³ R ⁴ R ⁵ one Mp 10-44 3-cl CF ₃ Cl N N N PINE ₃ one 10-45 3-CF ₃ CF ₃ Cl N N N PINE ₃ one 10-46 3,5- (CF ₃ ) ₂ CF ₃ Cl N N N PINE ₃ one 10-47 3,4,5-Cl ₃ CF ₃ Cl N N N PINE ₃ one 10-48 3,5-Me ₂ -4-NO ₂ CF ₃ Cl N N N PINE ₃ one 10-49 3-NO ₂ CF ₃ Cl N N N PINE ₃ one 10-50 3-CH ₃ CF ₃ Cl N N N PINE ₃ one 10-51 3-CH ₃ O CF ₃ Cl N N N PINE ₃ one 10-52 3-cn CF ₃ Cl N N N PINE ₃ one 10-53 3-CF ₃ O CF ₃ Cl N N N PINE ₃ one 10-54 3-CH ₃ S CF ₃ Cl N N N PINE ₃ one 10-55 3-CH ₃ S (O) CF ₃ Cl N N N PINE ₃ one 10-56 3-CH ₃ S (O) ₂ CF ₃ Cl N N N PINE ₃ one 10-57 3-CF ₃ S CF ₃ Cl N N N PINE ₃ one 10-58 3-CF ₃ S (O) CF ₃ Cl N N N PINE ₃ one 10-59 3-CF ₃ S (O) ₂ CF ₃ Cl N N N PINE ₃ one 10-60 3-OH CF ₃ Cl N N N PINE ₃ one 10-61 3-SH CF ₃ Cl N N N PINE ₃ one 10-62 3,5-Cl ₂ CF ₃ Cl CN N N PINE ₃ one 10-63 3,5-Cl ₂ CF ₃ Cl Me N N PINE ₃ one 10-64 3,5-Cl ₂ CF ₃ Cl Me Me N PINE ₃ one 10-65 3,5-Cl ₂ CF ₃ Cl cyclo-Pr N N PINE ₃ one 10-66 3,5-Cl ₂ CF ₃ Cl CF ₃ N N PINE ₃ one 10-67 3,5-Cl ₂ CF ₃ Cl CO ₂ Me N N PINE ₃ one 10-68 3,5-Cl ₂ CF ₃ Cl CH = CH ₂ N N PINE ₃ one

(X) m R Y R ² R ³ R ⁴ R ⁵ one Mp 10-69 3,5-Cl ₂ CF ₃ Cl CH ₂ CH ₂ N PINE ₃ one 10-70 3,5-Cl ₂ CF ₃ Cl CCH N N PINE ₃ one 10-71 3,5-Cl ₂ CF ₃ Br N N N COEt one 10-72 3,5-Cl ₂ CF ₃ Br N N N CO-n-Pr one 10-73 3,5-Cl ₂ CF ₃ Br N N N CO-iso-Pr one 10-74 3,5-Cl ₂ CF ₃ Br N N N Co-tert-bu one 10-75 3,5-Cl ₂ CF ₃ Br N N N COCF ₃ one 10-76 3,5-Cl ₂ CF ₃ Br N N N COPh one 10-77 3,5-Cl ₂ CF ₃ Br N N N CO-2-Pyridyl one 10-78 3,5-Cl ₂ CF ₃ Br N N N CO-3-Pyridyl one 10-79 3,5-Cl ₂ CF ₃ Br N N N CO-Pyridyl-CO-4 one 10-80 3,5-Cl ₂ CF ₃ Br N N N СО-2-F-С ₆ Н ₄ one 10-81 3,5-Cl ₂ CF ₃ Br N N N СО-3-F-С ₆ Н ₄ one 10-82 3,5-Cl ₂ CF ₃ Br N N N СО-4-F-С ₆ Н ₄ one 10-83 3,5-Cl ₂ CF ₃ Br N N N CO-2-Cl-C ₆ H ₄ one 10-84 3,5-Cl ₂ CF ₃ Br N N N CO-3-Cl-C ₆ H ₄ one 10-85 3,5-Cl ₂ CF ₃ Br N N N CO-4-Cl-C ₆ H ₄ one 10-86 3,5-Cl ₂ CF ₃ Br N N N CO-2-Br-C ₆ H ₄ one 10-87 3,5-Cl ₂ CF ₃ Br N N N СО-2-Ме-С ₆ Н ₄ one 10-88 3,5-Cl ₂ CF ₃ Br N N N SO-Vinyl one 10-89 3,5-Cl ₂ CF ₃ Br N N N SO-Propargil one 10-90 3,5-Cl ₂ CF ₃ Br N N N MeSO ₂ one 10-91 3,5-Cl ₂ CF ₃ Br N N N CF ₃ SO ₂ one

(X) m R Y R ² R ³ R ⁴ R ⁵ one Mp 10-92 3,5-Cl ₂ CF ₃ Br N N N CONHMe one 10-93 3,5-Cl ₂ CF ₃ Br N N N CONMe ₂ one 10-94 3,5-Cl ₂ CF ₃ Br N N N CO ₂ Me one 10-95 3,5-Cl ₂ CF ₃ Br N N N C (O) SMe one 10-96 3,5-Cl ₂ CF ₃ Br N N N CSMe one 10-97 3,5-Cl ₂ CF ₃ Br N N N CON (Me) -OMe one 10-98 3,5-Cl ₂ CH ₃ Br N N N PINE ₃ one 10-99 3,5-Cl ₂ CH ₃ CF ₃ N N N PINE ₃ one 10-100 3,5-Cl ₂ CH ₃ CN N N N PINE ₃ one 10-101 3,5-Cl ₂ CH ₃ NH ₂ N N N PINE ₃ one 10-102 3,5-Cl ₂ CH ₃ NHCOCH ₃ N N N PINE ₃ one 10-103 3,5-Cl ₂ CH ₃ NHCOCF ₃ N N N PINE ₃ one 10-104 3,5-Cl ₂ CH ₃ MNSO ₂ CH ₃ N N N PINE ₃ one 10-105 3,5-Cl ₂ CH ₃ NHCO ₂ CH ₂ -CCl ₃ N N N PINE ₃ one 10-106 3,5-Cl ₂ CH ₃ NHSO ₂ CH ₃ N N N PINE ₃ one 10-107 3,5-Cl ₂ CH ₃ NHSO ₂ CF ₃ N N N PINE ₃ one 10-108 3,5-Cl ₂ CH ₃ C = NOSH ₃ N N N PINE ₃ one 10-109 3,5-Cl ₂ CF ₃ Br N N N PINE ₃ 2 10-110 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ N N N PINE ₃ one 10-111 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ N N N SOS ₂ N ₅ one 10-112 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ N N N CO-cyclo-Pr one 10-113 3,4,5-Cl ₃ CF ₃ CF ₃ N N N PINE ₃ one 10-114 3,4,5-Cl ₃ CF ₃ CF ₃ N N N SOS ₂ N ₅ one 10-115 3,4,5-Cl ₃ CF ₃ CF ₃ N N N CO-cyclo-Pr one 10-116 3,4-Cl ₂ -CF ₃ CF ₃ CF ₃ N N N PINE ₃ one

Table 11

(X) m R Y T ⁴ Mp 11-1 3,5-Cl ₂ CF ₃ NO ₂ CO ₂ Me 11-2 3,5-Cl ₂ CF ₃ NO ₂ CO ₂ H 11-3 3,5-Cl ₂ CF ₃ NH ₂ CO ₂ Me 11-4 3,5-Cl ₂ CF ₃ F CO ₂ Me 11-5 3,5-Cl ₂ CF ₃ Cl CO ₂ Me 11-6 3,5-Cl ₂ CF ₃ Cl CO ₂ -tret-Bu 11-7 3,5-Cl ₂ CF ₃ Cl CO ₂ H 11-8 3,5-Cl ₂ CF ₃ Br CO ₂ Me 11-9 3,5-Cl ₂ CF ₃ I CO ₂ Me 11-10 3,5-Cl ₂ CF ₃ CH ₃ CO ₂ Me 11-11 3,5-Cl ₂ CF ₃ Cl CH ₃ 11-12 3,5-Cl ₂ CF ₃ CN F 11-13 3,5-Cl ₂ CF ₃ CH ₃ NO ₂ 11-14 3,5-Cl ₂ CF ₃ CH ₃ NH ₂ 11-15 3,5-Cl ₂ CF ₃ Br NO ₂ 11-16 3,5-Cl ₂ CF ₃ Br NH ₂ 11-17 3-CF ₃ CF ₃ NO ₂ CO ₂ Me 11-18 3-CF ₃ CF ₃ NO ₂ CO ₂ H 11-19 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CO ₂ Me 11-20 3,5- (CF ₃ ) ₂ CF ₃ NO ₂ CO ₂ H

(X) m R Y T ⁴ Mp 11-21 3,4-Cl ₂ CF ₃ NO ₂ CO ₂ Me 11-22 3,4-Cl ₂ CF ₃ NO ₂ CO ₂ H 11-23 3-cl CF ₃ NO ₂ CO ₂ Me 11-24 3-cl CF ₃ NO ₂ CO ₂ H 11-25 3,5-Br ₂ CF ₃ NO ₂ CO ₂ Me 11-26 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ Me 11-27 3,5-Me ₂ -4-NO ₂ CF ₃ NO ₂ CO ₂ Me 11-28 3-NO ₂ CF ₃ NO ₂ CO ₂ Me 11-29 3-CH ₃ CF ₃ NO ₂ CO ₂ Me 11-30 3-CH ₃ O CF ₃ NO ₂ CO ₂ Me 11-31 3-cn CF ₃ NO ₂ CO ₂ Me 11-32 3-CF ₃ O CF ₃ NO ₂ CO ₂ Me 11-33 3-CH ₃ S CF ₃ NO ₂ CO ₂ Me 11-34 3-CH ₃ S (O) CF ₃ NO ₂ CO ₂ Me 11-35 3-CH ₃ S (O) ₂ CF ₃ NO ₂ CO ₂ Me 11-36 3-CF ₃ S CF ₃ NO ₂ CO ₂ Me 11-37 3-CF ₃ S (O) CF ₃ NO ₂ CO ₂ Me 11-38 3-CF ₃ S (O) ₂ CF ₃ NO ₂ CO ₂ Me 11-39 3-OH CF ₃ NO ₂ CO ₂ Me 11-40 3-SH CF ₃ NO ₂ CO ₂ Me 11-41 3-NO ₂ CF ₃ NO ₂ CO ₂ H 11-42 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ H 11-43 2-cl CF ₃ NO ₂ CO ₂ Me 11-44 2-cl CF ₃ NO ₂ CO ₂ H 11-45 4-cl CF ₃ NO ₂ CO ₂ Me

(X) m R Y T ⁴ Mp 11-46 4-cl CF ₃ NO ₂ CO ₂ H 11-47 3,5-Cl ₂ CF ₃ CF ₃ CO ₂ Et 11-48 3,5-Cl ₂ CF ₃ CF ₃ CO ₂ H 11-49 3,5-Me ₂ -4-NO ₂ CF ₃ NO ₂ CO ₂ H 11-50 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ Me 11-51 3,5-Cl ₂ CF ₃ CN CO ₂ H 11-52 3,5-Cl ₂ CF ₃ CN CO ₂ Me 11-53 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ CO ₂ Et 11-54 3,5-Cl ₂ CF ₃ CF ₃ F 11-55 3,5-Cl ₂ CF ₃ CF ₃ NO ₂ 11-56 3,5-Cl ₂ CF ₃ CF ₃ NH ₂ 11-57 3,5-Cl ₂ CF ₃ F CO ₂ Et 11-58 3,4,5-Cl ₃ CF ₃ CF ₃ CO ₂ Et 11-59 3,4,5-Cl ₃ CF ₃ CF ₃ CO ₂ H

Table 12

(X) _m R Y T ⁴ Mp 12-41 3-CF ₃ S CF ₃ NO ₂ CO ₂ Me 12-42 3-CF ₃ S (O) CF ₃ NO ₂ CO ₂ Me 12-43 3-CF ₃ S (O) ₂ CF ₃ NO ₂ CO ₂ Me

(X) _m R Y T ⁴ Mp 12-44 3-OH CF ₃ NO ₂ CO ₂ Me 12-45 3-SH CF ₃ NO ₂ CO ₂ Me 12-46 3-NO ₂ CF ₃ NO ₂ CO ₂ H 12-47 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ H 12-48 2-cl CF ₃ NO ₂ CO ₂ Me 12-49 2-cl CF ₃ NO ₂ CO ₂ H 12-50 4-cl CF ₃ NO ₂ CO ₂ Me 12-51 4-cl CF ₃ NO ₂ CO ₂ H 12-52 3,5-Cl ₂ CF ₃ CF ₃ CO ₂ Me 12-53 3,5-Cl ₂ CF ₃ CF ₃ CO ₂ H 12-54 3,5-Me ₂ -4-NO ₂ CF ₃ NO ₂ CO ₂ H 12-55 3,4,5-Cl ₃ CF ₃ NO ₂ CO ₂ Me 12-56 3,5-Cl ₂ CF ₃ CN CO ₂ H 12-57 3,5-Cl ₂ CF ₃ CN CO ₂ Me 12-58 3,5- (CF ₃ ) ₂ CF ₃ CF ₃ CO ₂ Et 12-59 3,5-Cl ₂ CF ₃ CF ₃ F 12-60 3,5-Cl ₂ CF ₃ CF ₃ NO ₂ 12-61 3,5-Cl ₂ CF ₃ CF ₃ NH ₂ 12-62 3,5-Cl ₂ CF ₃ F CO ₂ Et 12-63 3,4,5-Cl ₃ CF ₃ CF ₃ CO ₂ Et 12-64 3,4,5-Cl ₃ CF ₃ CF ₃ CO ₂ H

Biological tests, example 1. Experience on the larvae of the common scoop Spodoptera litura

Solvent: 3 parts by weight of dimethylformamide; emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether.

To obtain the appropriate composition with the active substances, 1 part of the mass of the active substance is mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture is diluted with water to the desired concentration.

The leaves of sweet potato (sweet potato) are processed by immersion in the test solution diluted with water to the appropriate concentration, and after the solution is deposited on the leaves, they are dried in air, the resulting leaves are placed in laboratory cups with a diameter of 9 cm, into which 10 larvae of the common scoop are released at the third stage of development , and then the cups are set in a volume with controlled temperature at 25 ° C, while the sweet potato leaves are added to the cups on the second and fourth day of the study; insecticidal activity is calculated by counting the number of dead larvae after seven days.

The results are the average of two laboratory dishes for each group in this experiment.

Connections with numbers 1-3, 1-4, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-14, 1-15, 1-16, 1-22 , 1-23, 1-25, 1-54, 1-55, 1-56, 1-57, 1-63, 1-73, 1-75, 1-81, 1-83, 1-85.1 -86, 1-87, 1-88, 1-90, 1-91, 1-93, 2-8, 2-23, 2-29, 2-40, 2-41, 3-3 and 3-4 showed 100% mortality at an active substance concentration of 100 ppm.

Biological tests, example 2. Experience on a spider mite Tetranychus urticae (experience with spraying)

To obtain the appropriate composition with the active substance, 1 part of the mass of the active substance is mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture is diluted with water to the desired concentration.

From 50 to 100 adult ticks are transferred to the leaves of common beans in the stage of two leaves growing in a pot with a diameter of 6 cm. After one day, a large amount of diluted aqueous solution is sprayed with a pistol spray with an appropriate concentration of the active substance. After spraying, the pot is placed in the greenhouse for 7 days and the acaricidal activity is calculated using the following rating scale.

Acaricidal activity one hundred All processed ticks died 98 Survived (appeared as a result of reproduction) from 1 to 4 ticks 90 5 to 20 ticks survived (appeared as a result of reproduction) 60 Many ticks survived (appeared as a result of reproduction), but they are fewer than in the control experiment without treatment, several dead ticks are visible 0 No difference from control experience without treatment

Connections with numbers 1-3, 1-4, 1-7, 1-8, 1-9, 1-10, 1-12, 1-14, 1-15, 1-16, 1-17, 1-20 , 1-22, 1-23, 1-25, 1-54, 1-55, 1-56, 1-57, 1-75, 1-81, 1-84, 1-86, 1-87, 1 -90, 2-29, 3-3 and 3-4 showed acaricidal activity of more than 98% at an active substance concentration of 500 ppm.

Biological tests, example 3. Experience on Aulacophora femoralis (experience with spraying)

Solvent: 3 parts by weight of dimethylformamide.

Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether.

To obtain the appropriate composition with the active substances, 1 part of the mass of the active substance is mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture is diluted with water to the desired concentration.

Cucumber leaves are soaked in a diluted solution of the required concentration of the active compound, prepared as described in the previous experiment, dried in air and placed in a plastic cup containing black sterilized soil. 5 larvae of Aulacophora femoralis are released into this cup in the second phase of development. After 7 days, the number of dead larvae is calculated to calculate the insecticidal effect.

Connections with numbers 1-3, 1-4, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-14, 1-15, 1-16, 1-17 , 1-18, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-54, 1-55, 1-56, 1-57, 1-60, 1 -61, 1-80, 1-81, 1-85, 1-87, 1-88, 1-90, 1-91, 2-29, 3-3 and 3-4 showed a lethal insecticidal activity of 100% at a concentration active substances 100 ppm.

Biological tests, example 4. Experience on resistant against organophosphorus and carbamate derivatives peach aphid Myzus persicas

Solvent: 3 parts by weight of dimethylformamide.

Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether.

To obtain the appropriate composition with the active substances, 1 part of the mass of the active substance is mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture is diluted with water to the desired concentration.

About 30 to 50 adult Myzus persicas aphids with acquired resistance to organophosphorus and carbamate derivatives are transferred to one plant of eggplant seedlings at the stage of development of two leaves grown in pots with a diameter of 6 cm. One day after infection, a heavy spray is carried out using a spray gun the amount of diluted aqueous solution with an appropriate concentration of the active substance, while the solutions are prepared by analogy with the previous examples. After spraying, the pot is kept in the greenhouse for 7 days at 28 ° C, the percentage death rate is calculated. The experiment is repeated two times.

Compounds 1-7, 1-10, 1-14, and 1-16 showed a lethal activity of 98% at an active substance concentration of 500 ppm.

Biological tests, example 5. Experience on fleas Ctenocephalides felis

Solvent: dimethylformamide.

To prepare a suitable active compound formulation, 10 mg of the active compound is dissolved in 0.5 ml of the above solvent and the mixture is diluted to the appropriate concentration with the blood of domestic animals.

About 10 to 15 adult fleas of Ctenocephalides felis are placed in a special flea container. Another container containing blood with a solution of the substance obtained as described above is closed with a laboratory film (PARAFILM (Trademark)). The blood-containing container is turned upside down and placed on a special flea container. This system gives fleas the ability to suck blood in a container. A temperature of 37 ° C is maintained in the blood with the solution, and room temperature is maintained in a special flea container. After a certain period of time, the lethal effect on the fleas of Ctenocephalides felis is calculated. In this experiment, a 100% death rate means the death of all fleas of Ctenocephalides felis, while a 0% death rate means that all fleas survived.

In this biological experiment, compound 1-16 showed more than 80% mortality at an active ingredient concentration of 100 ppm.

Biological tests, example 6. Experience on ticks Boophilus microplus

Solvent: dimethylformamide.

To prepare a suitable active compound formulation, 10 mg of the active compound is dissolved in 0.5 ml of the above solvent and the mixture is diluted to the appropriate concentration with water.

The compound solution obtained by the above method is injected into the abdominal region of 5 fully saturated adult female Boophilus microplus. These Boophilus microplus ticks are transferred to the same cups and kept in a climatic chamber for a certain period of time.

After a certain time, the mortality rate among Boophilus microplus is calculated, and a 100% indicator means the death of all Boophilus microplus ticks, while a value of 0% corresponds to the survival of all ticks.

In this biological experiment, compound 1-16 showed more than 80% mortality at a dose of 20 μg of active ingredient per tick.

Biological tests, example 7. Experience on flies Lucillia cuprina

Solvent: dimethylformamide.

To prepare a suitable active compound formulation, 10 mg of the active compound is dissolved in 0.5 ml of the above solvent and the mixture is diluted to the appropriate concentration with water.

From about 20 to 30 larvae of Lucillia cuprina will be placed in a test tube containing 1 cm ^{3 of} crushed horse meat and 0.5 ml of the compound solution prepared by the above method.

After a certain period, the mortality of Lucillia cuprina is calculated. In this case, a 100% indicator means the death of all larvae of Lucillia cuprina, while a value of 0% corresponds to the survival of all larvae of flies.

In this biological experiment, compound 1-16 showed more than 80% mortality at an active substance concentration of 100 ppm.

Formulation Example 1 (granules)

To a mixture containing 10 parts of a compound of the invention, namely compound No. 1-3, 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of lignosulfonic acid salt, 25 parts of water are added, mixed thoroughly and granulated in a granulating extruder through a nozzle for sizes from 10 to 40 mesh; to obtain granules dried at a temperature of from 40 to 50 ° C.

Formulation Example 2 (Granules)

95 parts of clay mineral granules with a particle diameter distribution of 0.2 to 2 mm are placed in a rotary mixer, while rotating the mixer, they are evenly moistened with a sprayed mixture of liquid diluent and 5 parts of the compound of the invention, namely, compound No. 1-3, and dried at a temperature of from 40 to 50 ° C to obtain granules.

Formulation Example 3 (Emulsion)

To obtain an emulsion, 30 parts of the compound according to the invention are mixed, namely, compounds No. 1-3, 55 parts of xylene, 8 parts of polyethylene ethylene alkyl phenyl ether and 7 parts of calcium alkyl benzene sulfonate.

Formulation Example 4 (Wettable Powder)

15 parts of the compound according to the invention are mixed, namely Compound No. 1-3, 80 parts of a mixture of white carbon black (fine powder of hydrated amorphous silica) and powdered clay (1: 5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of the sodium salt of the alkyl naphthalene sulfonic acid condensation product and formaldehyde, the mixture is ground and a water-dispersible powder is obtained.

Formulation Example 5 (Wettable Granules)

Thoroughly mix 20 parts of the active compound according to the invention, namely compound No. 1-3, 30 parts of sodium ligninsulfonate, 15 parts of bentonite and 35 parts of calcined infusorized earth powder, water is added and then extruded through a sieve nozzle with 0.3 mm holes, dried and water dispersible granules are obtained.

Availability in industrial production.

Like insecticides, the novel arylpyrrolidines of the invention have excellent insecticidal effects, as shown in the above experiments.

Claims (7)

1. Arylpyrrolidines represented by formula (I)

,
where X, which may be the same or different, means halogen atoms, halogen-C _1-6 alkyl, nitro groups, C _1-6 alkyl, C _1-6 alkoxy, cyano groups, halogen-C _1-6 alkoxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, halo-C _1-6 alkylthio, halogen-C _1-6 alkylsulfinyl, halogen-C _1-6 alkylsulfonyl, hydroxyl groups, mercapto groups, amino groups, C _1-6 alkylcarbonylamino groups halogen-C _1-6 alkylcarbonylamino; C _1-6 alkoxycarbonylamino; halogen-C _1-6 alkoxycarbonylamino;
Y, which may be the same or different, means halogen atoms, halogen-C _1-6 alkyl, nitro groups, C _1-6 alkyl, C _1-6 alkoxy, cyano groups, halogen-C _1-6 alkoxy, C _1-6 alkylthio , C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, halo-C _1-6 alkylthio, halo-C _1-6 alkylsulfinyl, halogen-C _1-6 alkylsulfonyl, hydroxyl groups, mercapto groups, amino groups, C _1-6 alkylcarbonylamino groups, halogen-C _1-6 alkylcarbonyl-amino, C _1-6 alkoxycarbonylamino groups, halogen-C _1-6 alkoxycarbonylamino,
R is halogen-C _1-6 alkyl,
m takes values 0, 1, 2, 3, 4 or 5, n takes values 1, 2, 3 or 4, G is selected from the group consisting of

,
where R ¹ and R ² independently from each other each mean a hydrogen atom, unsubstituted C _1-6 alkyl, halogen-C _1-6 alkyl or a group CH ₂ -R ⁷ ,
R ³ and R ⁴ independently from each other each mean a hydrogen atom,
I takes the values 1, 2 or 3,
R ⁵ means a hydrogen atom,
R ⁶ means C _1-6 alkylcarbonyl,
or selected from the group consisting of heterocycles from G6 to G8:

where k ³ takes the values 0,
k ⁴ takes the values 0,
R ⁷ means an unsubstituted 6-membered heterocyclic aromatic ring with one nitrogen atom, and
And means a carbon atom or nitrogen. 2. An insecticidal composition comprising at least one compound according to claim 1. 3. A method for controlling insects and / or ticks, comprising the step of treating unwanted insects and / or ticks, and / or their habitat with the composition of claim 2. 4. The use of compounds according to claim 1 for controlling unwanted insects and / or ticks. 5. The use of compounds according to claim 1 for seed treatment in order to protect seeds and plant seedlings from pests. 6. Compounds represented by formula (II-a)

,
where the value of X is defined in claim 1, T ¹ means a hydrogen atom or a benzyl group, Hal-R means halogen C _1-6 alkyl and p takes the values 1, 2, 3, 4 or 5. 7. Compounds represented by formula (XXVIII)

where X, Y, R, A, m and n have the meanings given in claim 1 and T ⁴ means a cyano group, an amino group or a nitro group, or a group

,

,
where I, R ³ , R ⁴ , R ⁵ have the values given in claim 1,
R ⁸ means a hydrogen atom or C _1-6 acyl.