The present invention relates to novel dichloropropene derivatives, to a process for their preparation and to their use as insecticides.

It is already known that certain kinds of dihalogenopropene derivatives show an insecticidal action (cf. WO 96/15093, WO 01/44154, WO 03/42147, Japanese Laid-open Patent Publication No. 338668/1998, Japanese Laid-open Patent Publication No. 2001-335550).

There have now been found novel dichloropropene derivatives of the formula (I)

^=N- X— Y— Q ( I )

wherein

X represents a group -O-A1- or a group -N=A2-,

Y represents a single bond, O or S, or

X and Y together may represent O,

Q represents an aryl group that may be optionally substituted, a heterocyclic group that may be optionally substituted, or haloalkenyl,

m represents 2 or 3,

R1 represents halogen,

n represents 0 or 1 ,

A1 represents alkylene, alkylidene, alkenylene, cycloalkylene, alkylidenecycloalkyl, alkylene- oxyalkylene, alkyleneoxyiminoalkylidyne, alkan-yl-ylidene-iminooxyalkylene, alkan-yl- ylidene-iminooxyalkylidene or a group -(alkylene)-O(CO)NH-,

A2 represents alkylidyne, provided that , X and Y together represent O, in case that Q represents haloalkenyl, and X represents a group -O-A1- and Y represents a single bond or O, in case that Q represents a heterocyclic group that may be optionally substituted. The compounds of the formula (I), according to the invention, can be obtained by a process in which a) in case that X represents a group -O-A1-, Y represents a single bond, O or S and A1 represents alkylidene or alkenylene: compounds of the formula (II)

(H)

wherein m, R1 and n have the same definition as aforementioned, are reacted with compounds of the formula (III) Z-Ala-Ya-Q (IE) wherein Q has the same definition as aforementioned, Ala represents alkylidene or alkenylene, V represents a single bond, O or S, and Z represents halogen or alkylsulfonyl, in the presence of inert solvents, and if appropriate, in the presence of an acid binder, or b) in case that X represents a group -O-A1-, Y represents a single bond, O or S, or X and Y together may represent O, and A1 represents alkylene, alkyliden, cycloalkylene, alkylidene- cycloalkyl, alkan-yl-ylidene-iminooxyalkylene or alkan-yl-ylidene-iminooxyalkylidene: compounds of the formula (IV)

Cl

(IV)

wherein

m, R1 and n have the same definition as aforementioned,

are reacted with compounds of the formula (V)

H2N-Xb-Yb-Q (V)

wherein

Q has the same definition as aforementioned,

Xb represents a group -O-Alb-, Yb represents a single bond, O or S, or Xb and Yb together may represent O, and Alb represents alkylene, alkylidene, cycloalkylene, alkylidenecycloalkyl, alkan-yl-ylidene-iminooxyalkylene or alkan-yl-ylidene-iminooxyalkylidene,

in the presence of inert solvents, and if appropriate, in the presence of a catalyst,

or

c) in case that X represents a group -O-A1-, Y represents a single bond or O, n represents 0, and A1 represents alkylene or alkyleneoxyiminoalkylidyne:

compounds of the formula (VI)

Cl

b=N-C—A— OH (Vl)

wherein

m has the same definition as aforementioned, and Alc represents alkylene or alkyleneoxyiminoalkylidyne, are reacted with compounds of the formula (VII) HO-Q (VII) wherein Q has the same definition as aforementioned, or with compounds of the formula (VUT) Rc HON- ^Qc (vm) wherein R° represents alkyl, and Qc represents an aryl group that may be optionally substituted, in the presence of inert solvents, or d) in case that X represents a group -O-A1-, Y represents O, n represents 0, Q represents a heterocyclic group that may be optionally substituted, and A1 represents alkylene: compounds of the formula (DC)

1d N-O-A- OH (IX)

wherein m has the same definition as aforementioned, and Ald represents alkylene, preferably C2-C7-alkylene, are reacted with compounds of the formula (X) Z-Qd (X) wherein Z has the same definition as aforementioned, and Qd represents a heterocyclic group that may be optionally substituted, in the presence of inert solvents, and if appropriate, in the presence of an acid binder, or e) in case that X represents a group -O-A1-, Y represents a single bond, n represents 0, Q represents an aryl group that may be optionally substituted, and A1 represents a group -(alkylene)-O(CO)NH-: compounds of the aforementioned formula (DC) are reacted with compounds of the formula (XI) Qe-N=C=O (XI) wherein Qe represents an aryl group that may be optionally substituted, in the presence of inert solvent and if appropriate, in the presence of a catalyst, or f) in case that X represents a group -N=A2-, Y represents a single bond, n represents 0, Q represents an aryl group that may be optionally substituted, and A2 represents alkylidyne: compounds of the formula (XII)

(XIl)

wherein m has the same definition as aforementioned,

are reacted with compounds of the formula (XIH)

0 Q (XJS)

wherein

Qf represents an aryl group that may be optionally substituted, and

Rf represents alkyl,

in the presence of inert solvents, and if appropriate, in the presence of a catalyst.

All inventive compounds can be prepared by processes which are essentially the same as processes a) to f).

In the present specification:

"Halogen" represents fluorine, chlorine, bromine or iodine.

"Alkyl" can be straight chain or branched chain and there can be mentioned, for example, Ci^alkyl and specifically mentioned methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, etc. as examples.

"Alkoxy" represents a group alkyl-O-, whose alkyl part has the above-mentioned meaning and can be, for example, Ci^alkoxy, and there can be specifically mentioned methoxy, ethoxy, n- or iso- propoxy, n-, iso-, sec- or tert-butoxy, etc.

"Haloalkyl" represents straight chain or branched chain alkyl, at least one hydrogen of which was substituted with halogen. There can be mentioned, for example, Ci^alkyl substituted withl to 6 fluoro, chloro and/or bromo, and as their specific examples there can be mentioned fluoromethyl, chloromethyl, dichloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, chlorodifluoro- methyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-chloro-l,l,2-trifiuoroethyl, 3-fluoropropyl, 3- chloropropyl, 2,2,3,3,3-pentafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl, etc.

"Haloalkoxy" is a group haloalkyl-O-, whose haloalkyl part has the above-mentioned meaning and can be, for example, Ci ^haloalkoxy, and there can be specifically mentioned as "haloalkoxy", for example, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichloromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2,2,2-trifluoroethoxy, 3-chloropropoxy, etc.

As "alkylcarbonyl" there can be mentioned, for example, methylcarbonyl (namely, acetyl), ethylcarbonyl (namely, propionyl), etc.

As "alkoxycarbonyl" there can be mentioned, for example, methoxycarbonyl, ethoxycarbonyl, etc.

"Haloalkenyl" represents straight chain or branched chain alkenyl, at least one hydrogen of which was substituted with halogen and there can be mentioned, for example, 2-chloro-2-propenyl, 3- chloro-2-propenyl, 3,3-dichloro-2-propenyl, 4,4-difluoro-3-buten-l-yl, 3-chloro-4,4,4-trifluoro-2- butenyl, etc.

"Alkylene" can be straight chain or branched chain and there can be mentioned, for example, ethylene, trimethylene, methylethylene (propylene), tetramethylene, ethylethylene, penta- methylene, hexamethylene, etc.

"Alkylidene" can be straight chain or branched chain and there can be mentioned, for example, methylene, ethylidene, propylidene, isopropylidene, etc.

As "alkylidyne" there can be mentioned, for example, methylidyne, ethylidyne, propylidyne, etc.

As "alkenylene" there can be mentioned, for example, vinylene (namely, ethenylene), propenylene, 1-butenylene, 2-butenylene, etc.

As "cycloalkylene" there can be mentioned, for example, cyclopropylene, 1,2- or 1,3-cyclo- butylene, 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1 ,4-cyclohexylene, etc.

As "alkylene-cycloalkyl" there can be mentioned, for example, methylenecyclopropyl, ethylidene- cyclopropyl, etc.

As "alkyleneoxyalkylene" there can be mentioned, for example, ethyleneoxyethylene, propylene- oxypropylene, etc.

As "alkyleneoxyiminoalkylidyne" there can be mentioned, for example, ethyleneoxyimino- methylidyne, ethyleneoxyiminoethylidyne, etc.

As "alkan-yl-ylidene-iminooxyalkylene" there can be mentioned, for example, ethan-yl-ylidene- iminooxyethylene, ethan-yl-ylidene-iminooxypropylene, etc. As "alkan-yl-ylidene-iminooxyalkylidene" there can be mentioned, for example, ethan-yl-ylidene- iminooxymethylene, ethan-yl-ylidene-iminooxyethylidene, etc.

As "alkylene-O(CO)NH-" there can be mentioned, for example, -(ethylene)-O(CO)NH- etc.

As "aryl" there can be mentioned, for example, phenyl, 1-naphthyl, 2-naphthyl, 1,2,3,4-tetrahydro- 5-naphthyl (namely, tetralin-5-yl), l,2,3,4-tetrahydro-6-naphthyl (namely, tetralin-6-yl), etc.

As "5- or 6-membered heterocyclic group containing one or two hetero atoms selected from the group consisting of nitrogen atom and sulfur atom [said heterocyclic group may be condensed with benzene ring]" there can be mentioned, for example, monovalent groups derived from pyrrole, thiophene, pyrazole, imidazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, quinoline or isoquinoline, etc.

In the compounds of the aforementioned formula (I), preferably

X represents a group -O-A1- or a group -N=A2-,

Y represents a single bond, O or S, or

X and Y together may represent O,

Q represents phenyl group that may be optionally substituted [wherein substituents are at least one group selected from the group consisting of halogen, Q^alkyl, CMhaloalkyl, Ci^alkoxy, C^haloalkoxy, Q^alkyl-carbonyl, phenoxy that may be optionally halogen- substituted or Ci^haloalkyl-substituted, phenyl that may be optionally halogen-substituted, pyridyloxy that may be optionally Ci^haloalkyl-substiruted, cyano and nitro], naphthyl group that may be optionally substituted [wherein substituents are at least one group selected from the group consisting of halogen, C1-4alkoxy, C1-4alkoxy-carbonyl and nitro], 1,2,3,4-tetrahydronaphthyl group that may be optionally substituted [wherein substituents are at least one group selected from the group consisting of oxo and (phenyl that may be optionally Ci^haloalkyl-substituted)-methyloxyimino], a 5- or 6-membered heterocyclic group that may be optionally substituted and contains one or two hetero atoms selected from the group consisting of nitrogen atom and sulfur atom [wherein substituents are at least one group selected from the group consisting of Ci^alkyl, Ci^haloalkyl and nitro, and said heterocyclic group may be condensed with benzene ring] or C3.7haloalkenyl,

m represents 2 or 3,

R1 represents chlorine, n represents 0 or 1 ,

A1 represents C2-7alkylene, C1-6alkylidene, C2-7alkenylene, C3.7cycloalkylene, Ci.6alkylideneC3.7cycloalkyl, C2.7alkyleneoxyC2-7alkylene, C2-7alkyleneoxyiminoCi.6alkylidyne, C1-6alkan-yl-ylidene-iminooxyC2-7alkylene, C1-βalkan- yl-ylidene-iminooxyCi.6alkylidene or a group -(C2-7alkylene)-O(CO)NH-,

A2 represents C1-6alkylidyne,

provided that, X and Y together represent O, in case that Q represents C3-7haloalkenyl, and X represents a group -O-A1- and Y represents a single bond or O, in case that Q represents a 5- or 6- membered heterocyclic group that may be optionally substituted and contains one or two hetero atoms selected from the group consisting of nitrogen atom and sulfur atom [wherein substituents are at least one group selected from the group consisting of Ci^alkyl, Ci^haloalkyl and nitro, and said heterocyclic group may be condensed with benzene ring].

In the compounds of the aforementioned formula (I), particularly preferably

X represents a group -O-A1- or a group -N=A2-,

Y represents a single bond, O or S, or

X and Y together may represent O,

Q represents phenyl group that may be optionally substituted [wherein substituents are 1-4 groups selected from the group consisting of fluoro, chloro, bromo, iodo, methyl, sec- butyl, tert-butyl, trifluoromethyl, methoxy, n-butoxy, trifluoromethoxy, acetyl, phenoxy that may be optionally fluoro-substituted or trifluoromethyl-substituted, phenyl that may be optionally chloro-substituted, pyridyloxy that may be optionally trifluoromethyl- substituted, cyano and nitro], naphthyl group that may be optionally substituted [wherein substituents are 1-2 groups selected from the group consisting of chloro, bromo, methoxy, methoxycarbonyl and nitro], 1,2,3,4-tetrahydronaphthyl group that may be optionally substituted [wherein substituent is oxo or (trifluoromethyl-substituted phenyl)-methyloxy- imino], a heterocyclic group that may be optionally substituted [wherein said heterocyclic group is a monovalent group derived from a heterocycle selected from thiophene, pyrazole, pyridine and quinoline, and substituents are 1-2 groups selected from the group consisting of methyl, tert-butyl, trifluoromethyl and nitro], 3,3-dichloro-2-propen-l-yl or 4,4-difluoro- 3-buten-l-yl,

m represents 2 or 3, R1 represents chlorine,

n represents 0 or 1 ,

A1 represents ethylene, trimethylene, terramethylene, methylethylene, hexamethylene, methylene, ethylidene, propenylene, cyclohexylene, methylenecyclopropyl, ethylene- oxyethylene, ethyleneoxyiminoethylidyne, ethan-yl-ylidene-iminooxymethylene, ethan-yl- ylidene-iminooxyethylene, or group -CH2CH2-O(CO)NH-,

A2 represents methylidyne, provided that, X and Y together represent O, in case that Q represents 3,3-dichloro-2-propen-l-yl or 4,4-difluoro-3-buten-l-yl, and X represents a group -O-A1- and Y represents a single bond or O, in case that Q represents a heterocyclic group that may be optionally substituted [wherein said heterocyclic group is a monovalent group derived from a heterocycle selected from thiophene, pyrazole, pyridine and quinoline, and substituents are 1-2 groups selected from the group consisting of methyl, tert-butyl, trifluoromethyl and nitro].

The aforementioned preparation process (a) can be illustrated by the following reaction scheme in case that, for example, 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one oxime and 4- trifluoromethylbenzyl bromide are used as the starting materials.

CH2Br

base NOH

The aforementioned preparation process (b) can be illustrated by the following reaction scheme in case that, for example, 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one and O-{2-(4- trifluoromethylphenoxy)ethyl}hydroxylamine are used as the starting materials. CF; \ /rυ O^CH,CH,ONH0

O CH2CH2O

The aforementioned preparation process (c) can be illustrated by the following reaction scheme in case that, for example, 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(2-hydroxy- ethyl)-oxime and 2,4-difluorophenol are used as the starting materials.

_» : N-CO2C2H5 OCH2CH2OH Il 2 2 5 N-CO2C2H5 O CH2CH2O

The aforementioned preparation process (d) can be illustrated by the following reaction scheme in case that, for example, 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(2-hydroxy- ethyl)-oxime and 2-methanesulfonyl-5-trifluoromethyl-pyridine are used as starting materials.

CH, 3SWO~.2 ^ // CF, N- '

base N OCH2CH2OH 1 // \ O-CH2CH2O-// x^ CF, N The aforementioned preparation process (e) can be illustrated by the following reaction scheme in case that, for example, 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(2-hydroxy- ethyl)-oxime and 2-chlorophenyl isocyanate are used as the starting materials.

Cl

O J OCN

OCH2CH2OH 0-CH2CH2O(CO)NH

The aforementioned preparation process (f) can be illustrated by the following reaction scheme in case that, for example, {5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-ylide ne}-hydrazine and 4-trifluoromethylbenzaldehyde are used as the starting materials.

CHO

The compounds of the formula (JJ), starting materials in the above-mentioned preparation process (a), are novel compounds, that are not described in the existing literature yet, and can be easily prepared, for example, by reacting a compound of the aforementioned formula (IV) with a salt of hydroxylamine, for example, hydroxylamine hydrochloride etc., according to the process described in the literature, for example, Journal of Organic Chemistry, Vol.27, p.2841-2846 (1962); Journal of Heterocyclic Chemistry, Vol.20, p.239-240 (1983), etc.

The compounds of the above-mentioned formula (IV) are novel compounds, that are not described in the existing literature yet, and can be easily prepared, for example, by reacting a compound represented by the formula (XIV)

wherein

m, R1 and n have the same definition as aforementioned,

with 1,1,3-trichloropropene according to the process described in the literature, for example, Journal of the American Chemical Society, Vol.78, p.6101-6104 (1956) etc.

Among the compounds of the above-mentioned formula (XIV), the compounds, in which n represents 1, are novel compounds, that are not described in the existing literature yet, and can be easily prepared, for example, by reacting a compound, in which n represents 0, namely, per se known 4-hydroxy-l-indanone and 5-hydroxy-l-tetralone with a halogenating agent, for example, sulfuryl chloride .

The compounds of the formula (HI), starting materials in the above-mentioned preparation process (a), are per se known compounds.

As specific examples of the compounds of the formula (IT), used as starting materials in the above- mentioned preparation process (a), there can be mentioned the following:

5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one oxime,

2-chloro-5-(3,3-dichloro-allyloxy)-3 ,4-dihydro-2H-naphthalen- 1-one oxime,

4-(3 ,3-dichloro-allyloxy)-indan- 1-one oxime,

2-chloro-4-(3,3-dichloro-allyloxy)-indan-l-one oxime, etc.

As specific examples of the compounds of the formula (III), used as starting materials in the above-mentioned preparation process (a), there can be mentioned as follows:

benzyl bromide,

2-fluorobenzyl bromide,

3-fluorobenzyl bromide, 4-fluorobenzyl bromide, 2-chlorobenzyl bromide, 3-chlorobenzyl bromide, 4-chlorobenzyl bromide, 2-bromoben2yl bromide, 3-bromobenzyl bromide, 4-bromobenzyl bromide, 2-trifluoromethylbenzyl bromide, 3-trifluoromethylbenzyl bromide, 4-trifluoromethylbenzyl bromide, cinnamyl bromide 4-trifluoromethylcinnamyl bromide 2-methanesulfonyl-5-trifluoromethylpyridine, 3-chloro-2-methanesulfonyl-5-trifluoromethylpyridine, and so on. The compounds of the formula (V), starting materials in the above-mentioned preparation process (b), which are partly novel compounds that are not described in the existing literature yet, can be easily prepared, for example, from a compound represented by the formula Z"_Alb_γb_Q (XV) wherein Q, Alb and Yb have the same definition as aforementioned, Zb represents hydroxy or halogen, by reacting according to the process described in the literature, for example, Journal of Medicinal Chemistry, Vol.40, No.15, p.2363-2373 (1997); Agricultural and Biological Chemistry, Vol.49, No. l l, p.3197-3202 (1985), etc. The compounds of the above-mentioned formula (XV) are per se known compounds. As specific examples of the compounds of the formula (IV), used as starting materials in the above-mentioned preparation process (b), there can be mentioned as follows: 5-(l ,1-dichloro-proρen-3-yl)oxy-l-tetralone, 4-(l,l-dichloro-propen-3-yl)oxy-l-indanone, and so on. As specific examples of the compounds of the formula (V), used as starting materials in the above- mentioned preparation process (b), there can be mentioned as follows: O-phenylhydroxylamine, O-benzylhydroxylamine, O-(2-phenylethyl)hydroxylamine, 0-{2-(4-fluorophenyl)ethyl}hydroxylamine, O-{2-(4-trifluoromethylphenyl)ethyl}hydroxylamine, O-{2-{4-(4-trifluoromethylphenyl)oxyphenyl}ethyl}hydroxylami ne, O-{2-(4-bromophenyloxy)ethyl}hydroxylamine, O-(2-phenylthioethyl)hydroxylamine, O-(1-methyl-2-phenyl-ethyl)hydroxylamine, O-(2-phenoxypropyl)hydroxylamine, O-(2-phenyl-2-propyl)hydroxylamine, O-(3-phenylpropyl)hydroxylamine, O-{3-(4-fluorophenyl)propyl}hydroxylamine, O-{ 3-(4-trifluoromethylphenyl)propyl }hydroxylamine, O-{3-(4-fluorophenyloxy)propyl } hydroxylamine, 0-{3-(4-trifluoromethylphenyloxy)propyl}hydroxylamine, O-{ 3-(5-trifluoromethylpyridin-2-yloxy)propyl }hydroxylamine,

O-{4-(5-trifluoromethylpyridin-2-yloxy)butyl}hydroxylamin e,

O-{6-(4-fluorophenyloxy)hexyl } hydroxylamine,

0-{6-(5-trifluoromethylpyridin-2-yloxy)hexyl}hydroxylamin e,

O-(4-phenylcyclohexyl)hydroxylamine,

0-(2-phenyl-cyclopropylmethyl)hydroxylamine,

O-thiophen-2-ylmethyl-hydroxylamine,

O-thiophen-3-ylmethyl-hydroxylamine, and so on.

The compounds of the formula (VI), starting materials in the above-mentioned preparation process (c), are novel compounds, that are not described in the existing literature yet, and can be easily prepared, for example, by reacting a compound of the aforementioned formula (VI) with a compound represented by the formula

H2NO-Alc-OH (XVI)

wherein

Alc has the same definition as aforementioned,

according to the process described in the literature, for example, Chemical & Pharmaceutical Bulletin, Vol.31, No.8, p.2601-2606 (1983) etc.

The compounds of the aforementioned formula (XVI), which are partly novel compounds that are not described in the existing literature yet, can be easily prepared, for example, from a compound represented by the formula

HO-Alc-OH (XVJT)

wherein

Alc has the same definition as aforementioned,

by reacting according to the process described in the literature, for example, Journal of Medicinal Chemistry, Vol.13, No.3, p.398-403 (1970) etc. The compounds of the aforementioned formula (XVII) are per se known compounds. The compounds of the formula (VII), starting materials in the above-mentioned preparation process (c), are per se known compounds. As specific examples of the compounds of the formula (VI), used as starting materials in the above-mentioned preparation process (c), there can be mentioned as follows: 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(2-hydroxy-ethyl)-oxime, 4-(3,3-dichloro-allyloxy)-indan-l -one O-(2-hydroxy-ethyl)-oxime, 5-(3 ,3-dichloro-allyloxy)-3 ,4-dihydro-2H-naphthalen- 1-one O-(3-hydroxy-propyl)-oxime, 4-(3 ,3-dichloro-allyloxy)-indan- 1-one O-(3-hydroxy-propyl)-oxime, 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one 0-(4-hydroxy-butyl)-oxime, 4-(3,3-dichloro-allyloxy)-indan-l-one O-(4-hydroxy-butyl)-oxime, and so on. As specific examples of the compounds of the formula (VET), used as starting materials in the above-mentioned preparation process (c), there can be mentioned as follows: phenol, 2-methylphenol, 3-fluorophenol, 4-fluorophenol, 4-chlorophenol, 4-trifluoromethylphenol, 4-trifluoromethyloxyphenol, 2,4-difluorophenol, 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-trifluoromethylpyrimidin-5-ol, quinoline-6-ol, and so on.

The compounds of the formula (DC), starting materials in the above-mentioned preparation processes (d) and (e), are novel compounds, that are not described in the existing literature yet, and are included in the compounds of the aforementioned formula (VI).

The compounds of the formula (X), starting materials in the above-mentioned preparation process (d), are per se known compounds.

As specific examples of the compounds of the formula (X), used as starting materials in the above- mentioned preparation process (d), there can be mentioned as follows:

2-methanesulfonyl-5-trifluoromethylpyridine,

3-chloro-2-methanesulfonyl-5-trifluoromethylpyridine, and so on.

The compounds of the formula (XI), starting materials in the above-mentioned preparation process (e), are per se known compounds.

As specific examples of the compounds of the formula (XI), used as starting materials in the above-mentioned preparation process (e), there can be mentioned as follows:

2-chlorophenyl isocyanate,

3,4-dichlorophenyl isocyanate, and so on.

The compounds of the formula (KH), starting materials in the above-mentioned preparation process (f), are novel compounds, that are not described in the existing literature yet, and can be easily prepared, for example, by reacting a compound of the aforementioned formula (IV) with, for example, hydrazine hydrate according to the process described in the literature, for example, Journal of Organic Chemistry, Vol.60, No.15, p.4725-4729 (1995) etc.

The compounds of the formula (XHI), starting materials in the above-mentioned preparation process (f), are per se known compounds.

As specific examples of the compounds of the formula (XD), used as starting materials in the above-mentioned preparation process (f), there can be mentioned as follows:

{5-(3,3-dichloro-allyloxy)-3,4-dihyddro-2H-naphthalen-l-y lidene}hydrazine,

{4-(3,3-dichloro-allyloxy)-indan-l-ylidene}hydrazine, and so on. As specific examples of the compounds of the formula (XHI), used as starting materials in the above-mentioned preparation process (f), there can be mentioned as follows:

benzaldehyde,

2-bromobenzaldehyde,

3-chlorobenzaldehyde,

4-chlorobenzaldehyde,

4-trifluoromethylbenzaldehyde, and so on.

The reaction of the above-mentioned preparation process (a) can be conducted in an adequate diluent. As examples of the diluents used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA), etc.; sulfones, sulfoxides, for example, dimethyl sulfoxide (DMSO), sulfolane, etc.

The preparation process (a) can be conducted in the presence of an acid binder and as said acid binder there can be mentioned, as inorganic bases, hydrides, hydroxides, carbonates and bicarbonates, etc. of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide, etc.; as organic bases, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N- diethylamide, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc. The preparation process (a) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally about -50 to about 200"C, particularly about 0 to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.

In conducting the preparation process (a), the aimed compound can be obtained, for example, by reacting 0.1 to 10 moles of the compound of the formula (HI) to 1 mole of the compound of the formula (II) in a diluent, for example, acetonitrile, in the presence of potassium carbonate.

The reaction of the above-mentioned preparation process (b) can be conducted in an adequate diluent. As examples of the diluent used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.; esters, for example, ethyl acetate, amyl acetate, etc.

The preparation process (b) can be conducted in the presence of a catalyst and as examples of said catalyst there can be mentioned organic amine hydrochlorides, for example, pyridine hydro¬ chloride, triethylamine hydrochloride, etc.; amine sulfonates, for example, pyridine p- toluenesulfonate, triethylamine p-toluenesulfonate, etc.

The preparation process (b) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally about -50 to about 200°C, particularly about 0 to about 150°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.

In conducting the preparation process (b), the aimed compound can be obtained, for example, by reacting 0.5 to 2 moles of the compound of the formula (V) to 1 mole of the compound of the formula (FV) in a diluent, for example, ethanol, in the presence of, or without, pyridine p- toluenesulfonate.

The reaction of the above-mentioned preparation process (c) can be conducted in an adequate diluent. As examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc.

The preparation process (c) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally about -50 to about 2000C, particularly about 0 to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.

In conducting the preparation process (c), the aimed compound can be obtained, for example, by reacting 0.5 to 2 moles of a compound of the formula (VII) to 1 mole of the compound of the formula (DC) in a diluent, for example, dichloromethane, in the presence of triphenylphosphine and an azodicarboxylic acid ester.

The reaction of the above-mentioned preparation process (d) can be conducted in an adequate diluent. As examples of the diluents used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylformamide (DMF), dimethyl- acetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA), etc.; sulfones, sulfoxides, for example, dimethyl sulfoxide (DMSO), sulfolane, etc.; bases, for example, pyridine etc.

The preparation process (d) can be conducted in the presence of an acid binder and as said acid binder there can be mentioned, as inorganic bases, hydrides, hydroxides, carbonates and bicarbonates, etc. of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide, etc.; as organic bases, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethyl- aniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and l,8-diazabicyclo[5,4,0]ιmdec-7-ene (DBU), etc.; organolithium compounds, for example, methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, dimethyl copper lithium, lithium diisopropyl amide, lithium cyclohexyl isopropyl amide, lithium dicyclohexyl amide, n-butyl lithium -DABCO, n-butyl lithium -DBU, n-butyl lithium -TMEDA, etc.

The preparation process (d) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally about -50 to about 200°C, particularly about 0 to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.

In conducting the preparation process (d), the aimed compound can be obtained, for example, by reacting 0.5 to 2 moles of the compound of the formula (X) to 1 mole of the compound of the formula (IX) in a diluent, for example, dimethylformamide, in the presence of sodium hydride.

The reaction of the above-mentioned preparation process (e) can be conducted in an adequate diluent. As examples of the diluents used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc.

The preparation process (e) can be conducted in the presence of a catalyst and as examples of said catalyst there can be mentioned organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1 ,4-diazabicyclo[2,2,2]octane (DABCO) and l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.; organic amine hydrochlorides, for example, pyridine hydrochloride, triethylamine hydrochloride, etc.; amine sulfonates, for example, pyridine p-toluenesulfonate, triethylamine p-toluenesulfonate, etc.

The preparation process (e) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally about -50 to about 200°C, particularly about 0 to about 150°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.

In conducting the preparation process (e), the aimed compound can be obtained, for example, by reacting 0.5 to 2 moles of a compound of the formula (XI) to 1 mole of a compound of the formula (EX) in a diluent, for example, toluene, in the presence of4-dimethylaminopyridine (DMAP).

The reaction of the above-mentioned preparation process (f) can be conducted in an adequate diluent. As examples of the diluents used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.; esters, for example, ethyl acetate, amyl acetate, etc.

The preparation process (f) can be conducted in the presence of a catalyst and as examples of said catalyst there can be mentioned organic amine hydrochlorides, for example, pyridine hydro¬ chloride, triethylamine hydrochloride, etc.; amine sulfonates, for example, pyridine p-toluene- sulfonate, triethylamine p-toluenesulfonate, etc.

The preparation process (f) can be conducted in a substantially wide range of temperature. It is adequate to conduct it at the temperatures in a range of generally about -50 to about 200°C, particularly about 0 to about 150°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally also under elevated pressure or under reduced pressure.

In conducting the preparation process (f), the aimed compound can be obtained, for example, by reacting 0.5 to 2 moles of the compound of the formula (XIQ) to 1 mole of the compound of the formula (XII) in a diluent, for example, ethanol, in the presence of pyridine p-toluenesulfonate.

The compounds of the formula (I), according to the present invention, show strong insecticidal action. They can, therefore, be used as insecticides. And the active compounds of the formula (I), according to the present invention, exhibit exact controlling effect against harmful insects without giving phytotoxicity on the crops. And the compounds, according to the present invention, can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain pests, hygienic pests, etc. and applied for their extermination. As examples of such pests there can be mentioned the following pests:

As insects, there can be mentioned:

Coleoptera pests, for example,

Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Manochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus;

Lepidoptera pests, for example,

Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella;

Hemiptera pests, for example,

Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Tήaleurodes vaporariorum, Psylla spp., Bemisia argetifoli, Thrips palmi, Frankliniella occidentalis;

Orthoptera pests, for example,

Blatella germanica, Periplaneta americana, Gryllotalpa africana, Locusta migratoria migratoriodes;

Homoptera pests, for example,

Reticulitermes speratus, Coptotermes formosanus;

Diptera pests, for example,

Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, etc.

Moreover, as mites there can be mentioned, for example,

Tetranychus telarius, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp. etc. Furthermore, as nematodes there can be mentioned, for example,

Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides basseyi, Heterodera glycines, Pratylenchus spp. etc.

In addition, in the field of veterinary medicine, the novel compounds, according to the present invention, can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes. As examples of such animal-parasitic pests there can be mentioned the following pests:

As insects there can be mentioned, for example,

Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, etc.

As mites there can be mentioned, for example,

Ornithodoros spp., Ixodes spp., Boophilns spp., etc.

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

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

In the present invention substances having exterminating action against pests, which include all of them, are in some cases called insecticides. The active compounds, according to the present invention, can be formulated into customary formulation forms, when they are used as insecticides. As formulation forms there can be mentioned, for example, solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compounds, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc.

These formulations can be prepared by per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents or carriers; liquefied gas diluents or carriers; solid diluents or carriers, and optionally with surface-active agents, namely emulsifϊers and/or dispersants and/or foam-forming agents.

In case that water is used as extender, for example, organic solvents can also be used as auxiliary solvents.

As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols, etc.) or their ethers, esters, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), water, etc.

Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons, etc.

As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, artapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).

As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.) synthetic granules of inorganic or organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.) etc.

As emulsifϊers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers), alkylsulfonates, alkylsulfates, aryl- sulfonates, etc.], albumin hydrolysis products, etc.

Dispersants include, for example, lignin sulfite waste liquor, methyl cellulose, etc.

Tackiiϊers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).

Colorants can also be used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, zinc, etc.

Said formulations can contain the aforementioned active component of the amount in the range of generally 0.1 to 95 % by weight, preferably 0.5 to 90 % by weight.

The active compounds of the formula (I), according to the present invention, can exist also as a mixed agent with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators or herbicides in the forms of their commer¬ cially useful formulations or in the application forms prepared from such formulations. As the above-mentioned insecticides, there can be mentioned, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microorganisms, etc.

Further, the active compounds of the formula (I), according to the present invention, can exist also as a mixed agent with a synergist and such formulations and application forms can be mentioned as commercially useful. Said synergist itself must not be active, but is a compound that enhances the action of the active compound.

The content of an active compound of the formula (I), according to the present invention, in a commercially useful application form can be varied in a wide range.

The concentration of an active compound of the formula (I), according to the present invention, in use can be, for example, in the range of 0.0000001 to 100 % by weight, preferably 0.00001 to 1 % by weight.

The compounds of the formula (I), according to the present invention, can be applied by usual methods suitable to the application forms. In case of application against hygiene pests and pests of stored products, the active compounds of the present invention have a good stability against alkali on limed substrates and further show an excellent residual effectiveness in wood and soil.

As already mentioned above, it is possible to treat all plants or their parts in accordance with the invention. In a preferred embodiment, wild plant species or plant varieties and plant cultivars which have been obtained by traditional biological breeding methods, such as hybridization or protoplast fusion, and the parts of these varieties and cultivars are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by recombinant methods, if appropriate in combination with conventional methods (genetically modified organisms), and their parts are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.

Plants which are treated particularly preferably in accordance with the invention are those of the plant cultivars which are in each case commercially available or in use. Plant cultivars are understood as meaning plants with new traits which have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may take the form of cultivars, biotypes and genotypes.

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

The preferred transgenic plants or plant cultivars (those obtained by recombinant methods) to be treated in accordance with the invention include all those plants which, owing to the process of recombinant modification, were given genetic material which confers particular, advantageous, valuable traits to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to salinity in the water or soil, increased flowering performance, facilitated harvesting, accelerated maturation, higher yields, higher quality and/or higher nutritional value of the harvested products, better storage characteristics and/or processibility of the harvested products. Further examples of such traits, examples which must be mentioned especially, are better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses and an increased tolerance of the plants to certain herbicidal active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soybeans, potato, cotton, oilseed rape, beet, sugar cane and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis on maize, soybeans, potatoes, cotton and oilseed rape. Traits which are especially emphasized are the increased defence of the plants against insects, owing to toxins being formed in the plants, in particular toxins which are generated in the plants by the genetic material of Bacillus thuringiensis (for example by the genes CryΙA(a), CryIA(b), CryΙA(c), CryllA, CryEIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations; hereinbelow "Bt plants"). Other traits which are particularly emphasized are the increased defence of plants against fungi, bacteria and viruses by the systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Other traits which are especially emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example "PAT" gene). The genes which confer the desired traits in each case may also be present in the transgenic plants in combination with one another. Examples of "Bt plants" which may be mentioned are maize cultivars, cotton cultivars, soybean cultivars and potato cultivars which are commercially available under the trade names YIELD GARD® (for example maize, cotton, soybeans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize cultivars, cotton cultivars and soybean cultivars which are commercially available under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soybean), Liberty Link® (tolerance to phosphinothricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide- resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include also the varieties commercially available under the name Clearfield® (for example maize). Naturally, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars will be developed and/or marketed in the future.

The plants listed can be treated particularly advantageously with the compounds according to the invention or the active compound mixtures according to the invention.

Then the present invention will be described more specifically by examples. The present invention, however, should not be restricted only to them in any way. Synthesis Example 1 (Process a, Preparation of the compound No. 41)

While stirring 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one oxime (0.29g) together with dimethylformamide (5ml) under ice cooling, 60% sodium hydride (0.044g) was added thereto and stirred for 10 minutes, and after addition of 4-trifluoromethylbenzyl bromide (0.29g) the mixture was stirred at 40°C for 5 hours. The reaction mixture was poured into ice water and extracted by using ethyl acetate. The organic layer was washed with water and then with an aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 9:1) to obtain 5-(3,3-dichloro-allyloxy)-3,4- dihydro-2H-naphthalen- 1-one O-(4-trifluoromethylbenzyl)-oxime (0.35g) .

NMR: 1H-NMR (CDCl3) • 7.70-7.55 (3H,m), 7.50 (2H,d,J=8.1Hz), 7.12 (lH,t,J=8.1Hz), 6.76 (lH,d,J=8.1Hz), 6.16 (lH,t,J=6.1Hz), 5.26 (2H,s), 4.65 (2H,d,J=6.1Hz), 2.83-2.65 (4H,m), 1.89- 1.76 (2H,m).

The following compounds were prepared by similar processes to the above-mentioned Synthesis Example 1:

Compounds No. 1, 2, 3, 4, 5, 6, 7, 8, 23, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 55, 56, 57, 58, 59, 73, 145, 146. Synthesis Example 2 (Process b, Preparation of the compound No. 89)

O CH2CH2O

5-(3,3-Dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one (0.15g, O.55mmol) and O-{2-(4- trifluoromethylphenoxy)ethyl}hydroxylamine (0.14g, O.βlmmol) were dissolved in ethanol and the solution was stirred at room temperature for 24 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 9:1) to obtain 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-{2-(4- trifluoromethylphenoxy)ethyl}-oxime (0.21g, 88%).

1H-NMR (CDCl3) • 7.63 (lH,d,J=8.0Hz), 7.52 (2H,d,J=8.7Hz), 7.14 (lH,t,J=8.0Hz), 7.00 (2H,d,J=8.7Hz), 6.77 (lH,d,J=8.0Hz), 6.16 (lH,t,J=6.1Hz), 4.65 (2H,d,J=6.1Hz), 4.52 (2H,t,J=4.9Hz), 4.32(2H,t,J=4.9Hz), 2.70 (4H,t,J=6.3Hz), 1.79 (2H,t,J=6.3Hz).

The following compounds were prepared by similar processes to the above-mentioned Synthesis Example 2:

Compounds No. 9, 10, 11, 23, 53, 54, 60, 61, 62, 68, 69, 70, 71, 72, 79, 85, 141, 142, 143, 144, 147, 148, 149, 151, 154, 155, 156, 157, 158, 159, 160, 163, 164, 165, 166. Synthesis Example 3 (Process c, Preparation of the compound No. 100)

O CH2CH2O

5-(3,3-Dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(2-hydroxy-ethyl)-oxime (0.17g, 0.50mmol), 2,4-difluorophenol (52μl, 0.50mmol) and triphenylphosphine (0.16g, O.όOmmol) were dissolved in tetrahydrofuran (5ml) and diethyl azodicarboxylate (40% toluene solution) (0.26g, O.όOmmol) was added thereto at room temperature. After stirring the reaction mixture for 24 hours, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 9:1) to obtain 5-(3,3-dichloro- allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-{2-(2,4-difluorophenoxy)ethyl}-oxime (0.19g, 84%).

1H-NMR (CDCl3) • 7.62 (lH,d,J=8.1Hz), 7.14(lH,t,J=8.1Hz), 6.97 (lH,td,J=9.1, 5.3Hz), 6.89-6.69 (3H,m), 6.17 (lH,t,J=6.1Hz), 4.66 (2H,d,J=6.1Hz), 4.56-4.45 (2H,m), 4.32 (2H,t,J=4.8Hz), 2.75- 2.64 (4H,m), 1.86-1.72 (2H,m).

The following compounds were prepared by similar processes to the above-mentioned Synthesis Example 3:

Compounds No. 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 74, 75, 76, 77, 78, 80, 81, 82, 83, 84, 86, 87, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 127, 128, 129, 130, 131, 138, 139, 140. Synthesis Example 4 (Process d, Preparation of the compound No. 125)

O CH2CH2O- /T\ CF, N

While stirring 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(hydroxy-ethyl)- oxime (0.14g) and dimethylformamide (5ml) under ice cooling, 60% sodium hydride (0.02Ig) was added thereto and stirred for 10 minutes, and after addition of 2-methanesulfonyl-5-trifluoro- methyl-pyridine (0.115g) the reaction was conducted at 40°C for 5 hours. The reaction mixture was poured into cold water and extracted with ethyl acetate. The organic layer was washed with water and then with an aqueous solution of sodium chloride and dried. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 4:1) to obtain 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-{2-(5- trifluoromethyl-pyridin-2-yl)ethyl} -oxime (0.15g).

1H-NMR (CDCl3) ■ 8.42 (lH,s), 7.76 (lH,dd,J=8.8, 2.6Hz), 7.63 (lH,d,J=8.1Hz), 7.14 (lH,t,J=8.1Hz), 6.87 (lH,d,J=8.8Hz), 6.77 (lH,d,J=8.1Hz), 6.17 (lH,t,J=6.0Hz), 4.74-4.61 (4H,m), 4.55-4.48 (2H,m), 2.76-2.62 (4H,m), 1.87-1.72 (2H,m).

The following compounds were prepared by similar processes to the above-mentioned Synthesis Example 4:

Compounds No. 152, 153. Synthesis Example 5 (Process e, Preparation of the compound No. 161)

N I O-CH CH2O(CO)NH

5-(3,3-Dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one O-(2-hydroxy-ethyl)-oxime (0.15g), 2-

chlorophenyl isocyanate (0.085g) were reacted in tetrahydrofuran (5ml) in the presence of a catalytic amount of pyridine at 70°C for 4 hours. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3:1) to obtain 2-{5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-yli dene- aminoxy} -ethyl 2-chlorophenylcarbamate (0.18g).

NMR: 1H-NMR (CDCl3) • 8.14 (lH,t,J=9.3Hz), 7.64 (lH,d,J=8.1Hz), 7.40-6.96 (4H,m), 6.76

(lH,d,J=8.1Hz), 6.17 (lH,t,J=6.1Hz), 4.65 (2H,d,J=6.1Hz), 4.56-4.36 (4H,m), 2.84-2.59 (4H,m), 1.89-1.72 (2H,m).

The following compound was synthesized by a similar process to the above-mentioned Synthesis Example 5:

Compound No. 162. Svnthesis Example 6 (Process f, Preparation of the compound No. 67)

A solution of {5-(3,3-Dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-ylide ne}-hydrazine (0.2g) and 4-trifluoromethylbenzaldehyde (0.13g) in toluene (20ml) was stirred for 3 hours under heating and dehydrating azeotropically. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 9:1) to obtain N-{5-(3 ,3-dichloro-allyloxy)-3 ,4-dihydro-2H-naphthalen- 1-ylidene }-N '-(4-trifluoromethyl- benzylidene)hydrazine (0.2Ig).

NMR: 1H-NMR (CDCl3) ■ 8.43 (lH,s), 8.02-7.87 (3H,m), 7.68 (2H,d,J=8.3 Hz), 2.01-1.86 (lH,m), 6.87 (lH,d,J=7.9Hz), 6.19 (lH,t,J=6.1Hz), 4.69 (2H,d,J=6.1Hz), 2.97 (2H,t,J=6.3Hz), 2.81 (2H,t,J=6.3Hz), 1.98-1.89 (2H,m).

The following compounds were prepared by similar processes to the above-mentioned Synthesis Example 6:

Compounds No. 63, 64, 65, 66.

The compounds obtained in a similar manner to the above-mentioned Synthesis Examples 1 to 6 are shown, together with the compounds synthesized in the Synthesis Examples 1 to 6, in the following Table 1.

In case that m is 2 in the compounds of the formula (I), according to the present invention, the position number of the atoms in the ring is shown as in the following formula / (R1). and in case that m is 3 in the compounds of the formula (I), according to the present invention, the position number of the atoms in the ring is shown as in the following formula Cl =N— X— Y-Q 8 In Table 1, X1 represents group -OCH X2 represents group -O Q1 represents group Q2 represents group n-Bu represents n-butyl, s-Bu represents sec-butyl, t-Bu represents tert-butyl, Ph represents phenyl and PhO represents phenoxy.

Table 1

Cl

Comp. X Y Q m Physical (R1)- No. properties 1 O - CH2CH=CCl2 2 — 2 OCH2 - 4-Cl-Ph 2 — 3 OCH2 - 4-Br-Ph 2 — 4 OCH2 - 2-CF3-Ph 2 — 5 OCH2 — 3.-CF3-Ph - 2 — 6 OCH2 - 4-CF3-Ph 2 — 7 OCH2 - 2,4-Cl2-Ph 2 — 8 OCH2 - 2,4-(CF3)2-Ph 2 — 9 OCH(CH3) - Ph 2 — 10 OCH(CH3) - 4-CF3-Ph 2 - 11 O(CH2)2 - 4-CF3-Ph 2 — 12 O(CH2)2 O 4-F-Ph 2 — 13 O(CH2)2 O 4-Br-Ph 2 — 14 O(CH2)3 O 4-F-Ph 2 — 15 O(CH2)3 O 2-Cl-Ph 2 — 16 O(CH2)3 O 3-Cl-Ph 2 - 17 O(CH2)3 O 4-Cl-Ph 2 — 18 O(CH2)3 O 3-CF3-Ph 2 — 19 O(CH2)3 O 4-CF3-Ph 2 — 20 O(CH2)3 O 3,5-Cl2-Ph 2 — 21 O(CH2)3 O 5-CF3-pyridine-2-yl 2 - 22 0(CH2), O 5-CF3-pyridine-2-yl 2 — 23 O - CH2CH2CH=CF2 3 - 24 O - Ph 3 — 25 OCH2 - Ph 3 - Comp. X Y Q m (R')n Physical No. properties 26 OCH2 — 2-F-Ph 3 — 27 OCH2 — 3-F-Ph 3 — 28 OCH2 — 4-F-Ph 3 — 29 OCH2 — 2-Cl-Ph 3 — 30 OCH3 — 3-Cl-Ph 3 — 31 OCH2 — 4-Cl-Ph 3 — 32 OCH2 — 2-Br-Ph 3 — 33 OCH2 — 3-Br-Ph 3 — 34 OCH2 — 4-Br-Ph 3 — 35 OCH2 — 2-I-Ph 3 — 36 OCH2 — 3-I-Ph 3 — 37 OCH2 — 4-I-Ph 3 — 38 OCH2 — 4-CN-Ph 3 - 39 OCH2 — 2-CF3-Ph 3 — 40 OCH2 — 3-CF3-Ph 3 — 41 OCH2 — 4-CF3-Ph 3 — 42 OCH2 — 4-CF3-Ph 3 2-Cl 43 OCH2 — 4-OCF3-Ph 3 — 44 OCH2 — 2,3-F2-Ph 3 — 45 OCH2 — 2,4-F2-Ph 3 — 46 OCH2 — 2,6-F2-Ph 3 — 47 OCH2 — 3,5-F2-Ph 3 — 48 OCH2 — 2-F-4-Cl-Ph 3 — 49 OCH2 — 3,4-Cl2-Ph 3 — 50 OCH2 — 2,6-Cl2-Ph 3 — 51 OCH2 — 2,4,6-F3-Ph 3 — 52 OCH2 — 2,3,5,6-F4-Ph 3 — 53 OCH2 — thiophene-2-yl 3 — 54 OCH2 — thiophene-3-yl 3 — 55 OCH2 — 5-CF3-pyridine-2-yl 3 — 56 OCH2 — 1-naphthyl 3 — 57 OCH2 — 2-naphthyl 3 — 58 OCH2 O 4-Cl-Ph 3 — 59 OCH2 S Ph 3 — 60 OCH(CH3) — Ph 3 — 61 OCH(CH3) — 4-F-Ph 3 — 62 OCH(CH3) - 4-Cl-Ph 3 — 63 N=CH — Ph 3 — 64 N=CH — 3-Cl-Ph 3 — 65 N=CH — 4-Cl-Ph 3 - 66 N=CH — 2-Br-Ph 3 — 67 N=CH - 4-CF3-Ph 3 — 68 O(CH2)2 — Ph 3 — 69 O(CH2)2 - 4-F-Ph 3 — 70 O(CH2)2 — 4-CF3-Ph 3 — 71 O(CH2)2 — 4-(4-CF3-PhO)-Ph 3 - 72 O(CH2)2 - 3,5-(CF3)2-pyrazol-l-yl 3 - Comp. X Y Q m Physical (R1). No. properties 73 O(CH2)2 O Ph 3 — 74 O(CH2)2 O 2-CH3-Ph 3 — 75 O(CH2)2 O 3-CH3-Ph 3 — *1 76 O(CH2)2 O 4-CH3-Ph 3 — 77 O(CH2)2 O 2-F-Ph 3 — 78 O(CH2)2 O 3-F-Ph 3 — 79 O(CH2)2 O 4-F-Ph 3 — *2 80 O(CH2)2 O 2-Cl-Ph 3 — 81 O(CH2)2 O 3-Cl-Ph 3 — 82 O(CH2)2 O 4-Cl-Ph 3 — *3 83 O(CH2)2 O 2-Br-Ph 3 — 84 O(CH2)2 O 3-Br-Ph 3' — *4 85 O(CH2)2 O 4-Br-Ph 3 — 86 O(CH2)2 O 4-I-Ph 3 — 87 O(CH2)2 O 4-CN-Ph 3 — 88 O(CH2)2 O 3-CF3-Ph 3 — *5 89 O(CH2)2 O 4-CF3-Ph 3 — *6 90 O(CH2)2 O 4-s-Bu-Ph 3 — 91 O(CH2)2 O 4-t-Bu-Ph 3 — 92 O(CH2)2 O 4-OCH3-Ph 3 — 93 O(CH2)2 O 3-OCF3-Ph 3 - 94 O(CH2)2 O 4-OCF3-Ph 3 — *7 95 O(CH2)2 O 4-n-BuO-Ph 3 — 96 O(CH2)2 O 3-CH3CO-Ph 3 — 97 O(CH2)2 O 4-CH3CO-Ph 3 — 98 O(CH2)2 O 4-NO2-Ph 3 — 99 O(CH2)2 O 2,3-F2-Ph 3 — 100 O(CH2)2 O 2,4-F2-Ph 3 — *8 101 O(CH2)2 O 2,5-F2-Ph 3 — 102 O(CH2)2 O 2,6-F2-Ph 3 — 103 O(CH2)2 O 3,4-F2-Ph 3 — 104 O(CH2)2 O 3,5-F2-Ph 3 — 105 O(CH2)2 O 2,3-Cl2-Ph 3 — 106 O(CH2)2 O 2,4-Cl2-Ph 3 — 107 O(CH2)2 O 2,5-Cl2-Ph 3 — 108 O(CH2)2 O 2,6-Cl2-Ph 3 — 109 O(CH2)2 O 3,4-Cl2-Ph 3 — 110 O(CH2)2 O 3,5-Cl2-Ph 3 - 111 O(CH2)2 O 2-F-3-CF3-Ph 3 — *9 112 O(CH2)2 O 2-F-5-CF3-Ph 3 — 113 O(CH2)2 O 4-F-3-CF3-Ph 3 — *10 114 O(CH2)2 O 3,5-(CF3)2-Ph 3 — 115 O(CH2)2 O 2,3,5,6-F4-Ph 3 — 116 O(CH2)2 O 2-Ph-Ph 3 — 117 O(CH2)2 O 3-Ph-Ph 3 - 118 O(CH2)2 O 2-Cl-4-Ph-Ph 3 — 119 O(CH2)2 O 3-PhO-Ph 3 - Comp. X Y Q m (R1X, Physical No. properties 120 O(CH2)2 O 4-PhO-Ph 3 — 121 O(CH2)2 O 4.(4-F-PhO)-Ph 3 — 122 O(CH2)2 O 4-(pyridine-2-iloxy)Ph 3 — 123 O(CH2)2 O 4-(5-CF3-pyridine-2-iloxy)Ph 3 - 124 O(CH2)2 O pyridine-2-yl 3 — 125 O(CH2)2 O 5-CF3-pyridine-2-yl 3 — *11 126 O(CH2)2 O 5-NO2-pyridine-2-yl 3 — 127 O(CH2)2 O 2-CH3-pyridine-5-yl 3 - 128 O(CH2)2 O 2-CF3-pyrimidine-5-yl 3 — 129 O(CH2)2 O 2-t-Bu-pyrimidine-5-yl 3 - 130 O(CH2)2 O naphthalene- 1-yl 3 — 131 O(CH2)2 O naphthalene-2-yl 3 - 132 O(CH2)2 O 4-Cl-napythalene- 1-yl 3 — 133 O(CH2)2 O 6-CH3O-naphthalene-2-yl 3 - 134 O(CH2)2 O 6-CO2CH3-naphthalene-2-yl 3 — 135 O(CH2)2 O 2-NO2-naphthalene- 1-yl 3 — 136 O(CH2)2 O 1 ,6-Br2-naphthalene-2-yl 3 — 137 O(CH2)2 O l-tetralone-6-yl 3 - 138 O(CH2)2 O quinoline-6-yl 3 — 139 O(CH2)2 O Qi 3 - 140 O(CH2)2 O Q2 3 — 141 O(CH2)2 S Ph 3 - 142 OCH(CH3)CH2 — Ph 3 — 143 OCH(CH3)CH2 O Ph 3 - 144 OCH2CH(CH3) — Ph 3 — 145 OCH2CH=CH - Ph 3 - 146 OCH3CH=CH — 4-CF3-Ph 3 — 147 O(CH2)3 — Ph 3 — 148 O(CH2)3 — 4-F-Ph 3 — 149 O(CH2)3 — 4-CF3-Ph 3 — 150 O(CH2)3 O Ph 3 - 151 O(CH2)3 O 4-CF3-Ph 3 — 152 O(CH2)3 O 5-CF3-pyridine-2-yl 3 — 153 O(CH2)4 O 5-CF3-pyridine-2-yl 3 — 154 Xl — Ph 3 — 155 O(CH2)6 O 4-F-Ph 3 — 156 O(CH2)6 O 5-CF3-pyridine-2-yl 3 — 157 X2 — Ph 3 — 158 O(CH2)2O(CH2)2 O Ph 3 - 159 O(CH2)2O(CH2)2 O 4-F-Ph 3 — 160 OCH2CH2ON=C(CH — 4-Cl-Ph 3 - 161 OCH2CH2OCONH — 2-Cl-Ph 3 — 162 OCH2CH2OCONH — 3,4-Cl2-Ph 3 - 163 OCH2CH=NOCH2 - Ph 3 - 164 OCH2CH=NOCH2 — 4-CF3-Ph 3 — 165 OCH2CH=NOCH2C — Ph 3 — 166 OCH2CH=NOCH2C - 4-CF3-Ph 3 - *1 : Compound No. 75

1H-NMR (CDCl3) ■ 7.64 (IH, d, J= 7.2 Hz), 7.21-7.09 (2H, m), 6.81-6.69 (4H, m), 6.17 (IH, t, J = 6.1 Hz), 4.66 (2H, d, J = 6.1 Hz), 4.54-4.47 (3H, m), 4.26 (2H, t, J = 5.0 Hz), 2.77-2.65 (4H, m), 1.87-1.74 (2H, m).

*2: Compound No. 79

1H-NMR (CDCl3) ■ 7.63 (IH, d, J = 8.1 Hz), 7.14 (IH, t, J = 8.1 Hz), 7.02-6.83 (4H, m), 6.77 (IH, d, J = 8.1 Hz), 6.17 (IH, t, J = 6.1 Hz), 4.66 (2H, d, J = 6.1 Hz), 4.49 (2H, t, J = 5.0 Hz), 4.24 (2H, t, J = 5.0 Hz), 2.78-2.65 (4H, m), 1.86-1.72 (2H, m).

*3: Compound No. 82

1H-NMR (CDCl3) • 7.63 (IH, d, J = 8.1 Hz), 7.33-7.14 (3H, m), 6.87 (2H, d, J = 6.9 Hz), 6.77 (IH, d, J = 8.1 Hz), 6.17 (IH, t, J = 6.1 Hz), 4.66 (2H, d, J = 6.1 Hz), 4.50 (2H, t, J = 4.9 Hz), 4.25 (2H, t, J = 4.9 Hz), 2.72-2.69 (4H, m), 1.79 (2H, t, J = 6.2 Hz).

*4: Compound No. 84

1H-NMR (CDCl3) • 7.64 (IH, d, J = 7.9 Hz), 7.22-7.02 (4H, m), 6.87 (IH, d, J = 6.4 Hz), 6.77 (IH, d, J = 8.1 Hz), 6.17 (IH, t, J = 6.1 Hz), 4.65 (2H, d, J = 6.1 Hz), 4.50 (2H, t, J = 4.9 Hz), 4.26 (2H, t, J = 4.9 Hz), 2.76-2.65 (4H, m), 1.88-1.73 (2H, m).

*5: Compound No. 88

1H-NMR (CDCl3) • 7.64 (IH, d, J = 8.2 Hz), 7.39-7.10 (5H, m), 6.77 (IH, d, J = 8.2 Hz), 6.16 (IH, t, J = 6.1 Hz), 4.65 (2H, d, J = 6.1 Hz), 4.52 (2H, t, J = 4.8 Hz), 4.32 (2H, t, J = 4.8 Hz), 2.73-2.68 (4H, m), 1.81-1.79 (2H, m).

*6: Compound No. 89

1H-NMR (CDCl3) • 7.63 (IH, d, J = 8.0 Hz), 7.52 (2H, d, J = 8.7 Hz), 7.14 (IH, t, J = 8.0 Hz), 7.00 (2H, d, J = 8.7 Hz), 6.77 (IH, d, J = 8.0 Hz), 6.16 (IH, t, J = 6.1 Hz), 4.65 (2H, d, J = 6.1 Hz), 4.52 (2H, t, J = 4.9 Hz), 4.32 (2H, t, J = 4.9 Hz), 2.70 (4H, t, J = 6.3 Hz), 1.79 (2H, t, J = 6.3 Hz).

*7: Compound No. 94 1H-NMR (CDCl3) • 7.63 (IH, d, J = 8.1 Hz), 7.20-7.04 (3H, m), 6.92 (2H, d, J = 9.0 Hz), 6.77 (IH, d, J = 8.1 Hz), 6.16 (IH, t, J = 6.1 Hz), 4.65 (2H, d, J = 6.1 Hz), 4.51 (2H, t, J = 4.8 Hz), 4.27 (2H, t, J = 4.8 Hz), 2.78-2.59 (5H, m), 1.87-1.70 (2H, m).

*8: Compound No. 100

1H-NMR (CDCl3) • 7.62 (IH, d, J = 8.1 Hz), 7.14 (IH, t, J = 8.1 Hz), 6.97 (IH, td, J = 9.1, 5.3 Hz), 6.89-6.69 (3H, m), 6.17 (IH, t, J = 6.1 Hz), 4.66 (2H, d, J = 6.1 Hz), 4.56-4.45 (2H, m), 4.32 (2H, t, J = 4.8 Hz), 2.75-2.64 (4H, m), 1.86-1.72 (2H, m).

*9: Compound No. I l l

1H-NMR (CDCl3) • 7.62 (IH, d, J = 7.3 Hz), 7.21-7.10 (4H, m), 6.78 (IH, d, J = 7.3 Hz), 6.17 (IH, t, J = 6.1 Hz), 4.66 (2H, d, J = 6.1 Hz), 4.58-4.50 (2H, m), 4.39 (2H, t, J = 4.8 Hz), 2.74-2.62 (4H, m), 1.86-1.70 (2H, m).

*10: Compound No. 113

1H-NMR (CDCl3) • 7.63 (IH, d, J = 8.1 Hz), 7.20-7.02 (4H, m), 6.78 (IH, d, J = 8.1 Hz), 6.17 (IH, t, J = 6.1 Hz), 4.65 (2H, d, J = 6.1 Hz), 4.50 (2H, t, J = 4.8 Hz), 4.28 (2H, t, J = 4.8 Hz), 2.70 (4H, t, J = 6.5 Hz), 1.86- 1.73 (2H, m).

*11 : Compound No. 125

1H-NMR (CDCl3) • 8.42 (IH, s), 7.76 (IH, dd, J = 8.8, 2.6 Hz), 7.63 (IH, d, J = 8.1 Hz), 7.14 (IH, t, J = 8.1 Hz), 6.87 (IH, d, J = 8.8 Hz), 6.77 (IH, d, J = 8.1 Hz), 6.17 (IH, t, J = 6.0 Hz), 4.74-4.61 (4H, m), 4.55-4.48 (2H, m), 2.76-2.62 (4H, m), 1.87-1.72 (2H, m).

Synthesis Example 7 (Preparation of an intermediate)

NOH 5-(3,3-Dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one (4.Og, 14.8mmol), hydroxylamine hydrochloride (2.1g, 29.5mmol) and sodium hydrogen carbonate (2.5g, 29.5mmol) were mixed and stirred in ethanol (60ml) at room temperature for 6 hours. After distilling off the solvent under reduced pressure, water (50ml) was added to the residue and extracted with ethyl acetate (100ml). The organic layer was dried with anhydrous magnesium sulfate and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = gradient eluted from 3:1 to 2:1) to obtain 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l- one oxime (3.9g, 92%).

1H-NMR (CDCl3) • 7.71 (lH,s), 7.57 (lH,d,J=8.1Hz), 7.16 (lH,t,J=8.1Hz), 6.79 (lH,d,J=8.1Hz), 6.18 (lH,t,J=6.2Hz), 4.67 (2H,d,J=6.2Hz), 2.83-2.69 (4H,m), 1.92-1.79 (2H,m).

Synthesis Example 8 (Preparation of an intermediate)

5-Hydroxy-3,4-dihydro-2H-naphthalen-l-one (5.0g, 30.8mmol) and about 65% pure sodium hydride (1.7Ig, 46mmol) were dissolved in a mixed solution of tetrahydrofuran (80ml) and N,N- dimethylformamide (40ml), and 1,1,3-trichloropropene (10.8g, purity 60%) was added thereto at room temperature. After stirring for 3 hours, water was added to the reaction solution. The mixture was extracted with ether (100ml) and dried with anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by column chromatography to obtain 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one (8.0g, 96%).

1H-NMR (CDCl3) • 7.69 (lH,d,J=7.9Hz), 7.27 (lH,t,J=7.9Hz), 6.98 (lH,d,J=7.9Hz), 6.18 (lH,t,J=6.1Hz), 4.70 (2H,d,J=6.1Hz), 2.90 (2H,t,J=6.2Hz), 2.63 (2H,t,J=6.5Hz), 2.19-2.06 (2H,m).

Synthesis Example 9 (Preparation of an intermediate)

OCH2CH2ONH2 4-Hydroxybenzotrifluoride (6.1g, 37.6mmol), ethylene glycol (8.4ml, 150mmol) and triphenyl- phosphine (12.8g, 48.8mmol) were dissolved in tetrahydrofuran (80ml) and diethyl azo- dicarboxylate (40% toluene solution) (21.Og, 48.8mmol) was added thereto at room temperature. After stirring the mixture for 24 hours, the solvent was distilled off and the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3:1) to obtain 2-(4-trifluoro- methylphenoxy)-ethanol (2.2g, 28%).

To the obtained 2-(4-trifluoromethylphenoxy)-ethanol, N-hydroxyphthalimide (2.1g, 12.7mmol) and triphenylphosphine (3.6g, 13.8mmol) were added and the mixture was dissolved in tetra¬ hydrofuran (25ml). Diethyl azodicarboxylate (40% toluene solution) (6.Og, 13.8mmol) was further added thereto at room temperature. After stirring the mixture for 24 hours, the solvent was distilled off and the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 2:1) to obtain 2-[2-(4-trifluoromethylphenoxy)-ethoxy]isoindole-l,3-dione (2.6g, 70%).

1H-NMR (CDCl3) • 7.89-7.73 (2H,m), 7.52 (lH,d,J=8.5Hz), 6.90 (lH,d,J=8.5Hz), 4.60 (lH,t,J=5.6Hz), 4.40 (lH,t,J=5.6 Hz).

The obtained 2-[2-(4-trifluoromethylphenoxy)-ethoxy]isoindole-l,3-dione was dissolved in ethanol (40ml) and hydrazine hydrate (0.47ml, 9.6mmol) was added thereto. After stirring the mixture at room temperature for 24 hours, the solvent was distilled off under reduced pressure. Ether was added to the residue and the precipitate was removed by filtration. The solvent was distilled off under reduced pressure to obtain O-{2-(4-fluorophenoxy)-ethyl}hydroxylamine (1.4g, 85%).

1H-NMR (CDCl3) - 7.54 (lH,d,J=8.4Hz), 6.99 (lH,d,J=8.4Hz), 5.54 (IH, br s), 4.23-4.17 (lH,m), 4.06-4.00 (lH,m).

Synthesis Example 10 (Preparation of an intermediate)

OCH2CH2OH After refluxing 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one (2.7g), 2-aminooxy- ethanol (1.4g) and pyridinium p-toluenesulfonate (O.lg) in ethanol (50ml) for 3 hours, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 7:3) to obtain 5-(3,3-dichloro-allyloxy)-3,4- dihydro-2H-naphthalen-l-one O-(2-hydroxyethyl)-oxime (2.5g).

NMR: 1H-NMR (CDCl3) ■ 7.56 (lH,d,J=8.1Hz), 7.14 (lH,t,J=8.1Hz), 6.78 (lH,d,J=8.1Hz), 6.17 (lH,t,J=6.1Hz), 4.66 (2H,d,J=6.1Hz), 4.38-4.26 (3H,m), 4.01-3.89 (3H,m), 2.81-2.68 (5H,m), 1.91- 1.76 (3H,m).

Synthesis Example 11 (Preparation of an intermediate)

5-(3,3-Dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-one (2.3g) and 55% hydrazine hydrate (1.23g) were refluxed in ethanol (50ml) for 3 hours. After concentrating the reaction mixture to about 1/3 by distilling off the solvent under reduced pressure, it was cooled and the deposited solid was filtered to obtain { 5-(3,3-dichloro-allyloxy)-3,4-dihydro-2H-naphthalen-l-yliden e}-hydrazine (1.5g).

It was used for a next reaction without further purification. Biological Test Example 1 : Test against larva ofSpodoptera litura

Preparation of test solution:

Solvent: Dimethylformamide 3 parts by weight

Emulsifier: Polyoxyethylene alkyl phenyl ether 1 part by weight

In order to make an appropriate formulation of an active compound, 1 part by weight of the active compound was mixed with the above-mentioned amount of solvent containing the above- mentioned amount of emulsifier and the mixture was diluted with water to a prescribed concentration.

Test method:

Leaves of sweet potato were soaked in the test solution diluted to a prescribed concentration with water, dried in the air and put in a dish of 9 cm diameter. 10 larvae of Spodoptera litura at the third instar were placed thereon and kept in a room at the constant temperature of 25°C. After 2 and 4 days further leaves of sweet potato were added and after 7 days the number of dead larvae was counted and the rate of death was calculated.

In this test the results of 2 dishes at 1 section were averaged.

Test results

As specific examples the compounds of the compound No. 75, 79, 82, 84, 88, 89, 94, 100, 111, 113 and 125 showed 100% of rate of death at lOOppm concentration of the active component.

Formulation Example 1 (Granule)

To a mixture of the compound of the present invention No. 125 (10 parts), bentonite (mont- morillonite) (30 parts), talc (58 parts) and ligninsulfonate salt (2 parts), water (25 parts) was added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40- 500C to obtain granules.

Formulation Example 2 (Granules)

Clay mineral particles having particle diameter distribution in the range of 0.2-2mm (95 parts) are put in a rotary mixer. While rotating it, the compound of the present invention No.125 (5 parts) is sprayed together with a liquid diluent, wetted uniformly and dried at 40-500C to obtain granules. Formulation Example 3 (Emulsifiable concentrate)

The compound of the present invention No.125 (30 parts), xylene (5 parts), polyoxyethylene alkyl phenyl ether (8 parts) and calcium alkylbenzenesulfonate (7 parts) are mixed and stirred to obtain an emulsifiable concentrate.

Formulation Example 4 (Wettable powder)

The compound of the present invention No.125 (15 parts), a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5) (80 parts), sodium alkyl¬ benzenesulfonate (2 parts) and sodium alkylnaphthalenesulfonate-formalin-condensate (3 parts) are mixed in powder form to make a wettable powder.

Formulation Example 5 (Water dispersible granule)

The compound of the present invention No.125 (20 parts), sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.