KR100346161B1 - 3-Aryl-4-hydroxy-△3-dihydrofuranone derivatives - Google Patents

Abstract

The present invention relates to 3-aryl-4-hydroxy- -Dihydrofuranone derivatives, various methods of making them, and their use as pesticides.

In this formula,

A, B, G, X, Y, Z and n are as defined in the specification.

Description

3-Aryl-4-hydroxy-Δ 3-dihydrofuranone derivatives {3-Aryl-4-hydroxy-Δ 3-dihydrofuranone derivatives}

The present invention relates to novel 3-aryl-4-hydroxy- -Dihydrofuranone derivatives, processes for their preparation and their use as pesticides.

Some substituted -Dihydrofuran-2-one derivatives have herbicidal properties (see DE-A 4,014,420). DE-A 4,014,420 also discloses the use of starting compounds (for example 3- (2-methylphenyl) -4-hydroxy-5- (4- fluorophenyl) -Dihydrofuran-2-one). ≪ / RTI > Compounds with similar structures are described in Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985 , (8) 1567-76, but does not indicate insecticidal and / or salivary activity. EP 528,156 also discloses 3-aryl-pyrimidine compounds having herbicidal, -Dihydrofuranone derivative, the activity described in the patent is not always satisfactory.

According to the invention, novel 3-aryl-4-hydroxy- -Dihydrofuranone derivatives and compounds of the general formula (I) in stereomerically and enantiomerically pure forms have been found.

In this formula,

X represents alkyl, halogen, alkoxy or halogenoalkyl,

Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl,

Z represents alkyl, halogen or alkoxy,

n represents a number of 0 to 3,

Lt; RTI ID = 0.0 > X < / RTI > and Z, together with the phenyl radical to which they are attached,

(Where Y is as defined above) to form a naphthalene radical,

G is hydrogen (a) or group

Lt; / RTI >

A and B form an alkoxy, alkylthio, sulfonic poksil, alkylsulfonyl, carboxyl, or a cycle substituted by a C0 ^₂ R _2, together with the carbon atom to which they are attached, or

A and B together with the carbon atoms to which they are attached form a cycle wherein two substituents together with the carbon atoms to which they are attached are optionally substituted by alkyl, alkoxy or halogen and which may be interrupted by oxygen or sulfur Represents a saturated cycle,

Represents one equivalent of a metal ion or ammonium ion,

L and M represent in each case oxygen or sulfur,

R ¹ is an optionally substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, or cycloalkyl which may be interrupted by at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl , ≪ / RTI > hetaryl, phenoxyalkyl or hetaryloxyalkyl,

R < ² > each independently represent optionally substituted alkyl, cycloalkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl; Phenyl or benzyl, in each case optionally substituted,

R ³ , R ⁴ and R ⁵ independently of one another are each independently alkyl optionally substituted by halogen, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, alkynylthio or cycloalkylthio, Substituted phenyl, phenoxy or phenylthio,

R ⁶ and R ⁷ independently of one another represent hydrogen or represent alkyl, alkenyl, alkoxy or alkoxyalkyl, in each case optionally substituted by halogen, optionally substituted phenyl, or optionally substituted benzyl,

R ⁶ and R ⁷ together represent an alkylene radical optionally interrupted by oxygen or sulfur.

When the definition of the group G of the general formula (I) is (a), (b), (c), (d), (e), (f) (Ig).

In this formula,

A, B, E, L, M, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n have the abovementioned meanings.

Further, according to the present invention,

(A)

An intramolecular condensation reaction is carried out with respect to the carboxylic acid ester of formula (II) in the presence of a diluent and in the presence of a base to give 3-aryl-4-hydroxy- - < / RTI > dihydrofuranone derivative of formula (I).

In this formula,

A, B, X, Y, Z and n have the abovementioned meaning,

R ⁸ represents alkyl.

(B)

Further, according to the present invention,

Compounds of formula (Ia)

(a) optionally in the presence of a diluent and optionally in the presence of an acid-binding agent, with an acid halide of formula (III)

(β) optionally in the presence of a diluent and optionally in the presence of an acid-binding agent, with a carboxylic acid anhydride of general formula (IV)

A process for preparing the compound of formula (Ib) has been found.

In this formula,

A, B, X, Y, Z, R ¹ and n have the above-mentioned meanings.

(C)

Further, according to the present invention,

The compound of formula (Ia) is reacted with a chloroformic ester or chloroformic acid ester of formula (V) optionally in the presence of a diluent and optionally in the presence of an acid-binding agent to give a compound of formula (Ic) A method for producing a compound has been found.

In this formula,

A, B, X, Y, Z, R ² and n have the above-

L represents oxygen,

M represents oxygen or sulfur.

(D)

Further, according to the present invention,

The compound of formula (Ia) is reacted with a chloromonothioformic ester or chlorodithioformic ester of the formula (VI) optionally in the presence of a diluent and optionally in the presence of an acid-binding agent to give a compound of the formula Lt; RTI ID = 0.0 > Ic) < / RTI >

In this formula,

A, B, R < ² >, X, Y, Z and n have the above-

L represents sulfur,

M represents oxygen or sulfur.

(E)

Further, according to the present invention,

A process for preparing a compound of formula (Id) by reacting a compound of formula (Ia), optionally in the presence of a diluent, and optionally in the presence of an acid-binding agent, with a sulfonyl chloride of formula (VII) .

In this formula,

A, B, X, Y, Z, R ³ and n have the abovementioned meanings.

(F)

Further, according to the present invention,

A process for the preparation of a compound of formula (Ie) by reaction of a compound of formula (Ia), optionally in the presence of a diluent, and optionally in the presence of an acid-binding agent, with a phosphorus compound of formula (VIII) lost.

In this formula,

A, B, L, X, Y, Z, R ⁴ , R ⁵ and n have the above-

Hal represents halogen, especially chlorine or bromine.

(G)

Further, according to the present invention,

Compounds of formula (Ia)

(α) optionally in the presence of a diluent and optionally in the presence of a catalyst, with an isocyanate of general formula (IX)

(If), optionally in the presence of a diluent, and optionally in the presence of an acid-binder, with a carbamoyl chloride or thiocarbamoyl chloride of general formula (X) to give the compounds of formula (If) It turned out.

In this formula,

A, B, L, X, Y, Z, R ⁶ , R ⁷ and n have the above-mentioned meanings.

(H)

Further, according to the present invention,

It has been found that a compound of formula (Ia) is prepared by reacting a compound of formula (Ia) with a metal compound or amine of formula (XI) and (XII), optionally in the presence of a diluent.

In this formula,

X, Y, Z, A, B and n have the abovementioned meaning,

Represents one equivalent of a metal ion or ammonium ion,

Me represents a monovalent or divalent metal ion,

t represents a number of 1 or 2,

R ⁹ represents hydrogen, hydroxy or alkoxy,

R ¹⁰ , R ¹¹ and R ¹² independently represent hydrogen or alkyl.

Also according to the present invention there is provided a novel 3-aryl-4-hydroxy- -Dihydrofuranone derivatives exhibit salicidal activity, insecticidal activity and herbicidal activity and thus are suitable for use as pesticides.

Preferred compounds of the compounds of formula (I)

X is C _l-6 - represents a halogeno-alkyl, -alkyl, halogen, C _1-6 - alkoxy or C _1-3

Y represents hydrogen, C _1-6 -alkyl, halogen, C _1-6 -alkoxy or C 1- ₃ -halogenoalkyl,

Z represents C _1-6 -alkyl, halogen or C _1-6 -alkoxy,

n represents a number of 0 to 3,

Lt; RTI ID = 0.0 > X < / RTI > and Z, together with the phenyl radical to which they are attached,

(Wherein Y is as defined above) to form a naphthalene radical,

A and B are C _l-6, together with the carbon atom to which they are attached -alkoxy, C _1-4 - alkylthio, C _l-4-sulfonic poksil alkyl, C _{1-4-alkylsulfonyl,} carboxyl, or CO ₂ R ² To form a saturated or unsaturated 3- to 8-

A and B together with the carbon atoms to which they are attached form a C _{3-8 -cycle} wherein two substituents together with the carbon atoms to which they are attached represent C _1-6 -alkyl, C _1-6 -alkoxy or A saturated C _5-7 -ring optionally substituted by halogen and which may be interrupted by oxygen or sulfur,

G is hydrogen (a) or group

Represents the

here,

Represents one equivalent of a metal ion or ammonium ion,

L and M represent in each case oxygen or sulfur,

R ¹ is an optionally halogen in each case substituted C _1-20 - alkyl, C _2-20 - alkenyl, C _l-8-alkoxy -C _1-8 - alkyl, C _{l-8-alkylthio} -C _{l 8} - alkyl, C _{l-8-alkoxy poly-l} -C ₈ -alkyl, or halogen or a C _l-6-alkyl optionally substituted by C, which may be interrupted by at least one oxygen and / or sulfur atoms _3-8 -cycloalkyl:

Phenyl optionally substituted by halogen, nitro, C _1-6 -alkyl, C _1-6 -alkoxy, C _1-6 -halogenoalkyl or C _1-6 -halogenoalkoxy;

Halogen, C _l-6 - alkyl, C _l-6 - alkoxy, C _l-6 - halogenoalkyl or C _l-6 - halogenoalkyl the alkoxy by optionally substituted phenyl -C _1-6 - alkyl;

Hetaryl optionally substituted by halogen and / or Ci- ₆ -alkyl;

Phenoxy-C _1-6 -alkyl optionally substituted by halogen and / or C _1-6 -alkyl; or

Halogen, amino and / or C _1-6 - alkyl optionally substituted by a _{hat-aryloxy-l} -C ₆ - represents an alkyl,

R ² is a halogen in each case optionally substituted by C _l-20 - alkyl, C _3-20 - alkenyl, C _l-8 - alkoxy -C _2-8 - alkyl, C _l-8 - poly alkoxy -C _2-8 -alkyl,

Halogen or C _l-6 - alkyl optionally substituted by a C _3-8 - cycloalkyl, or

Halogen, nitro, C _1-6 -alkyl, C _1-6 -alkoxy, C _1-6 -halogenoalkyl, phenyl or benzyl,

R ^3, R ⁴ and R ⁵ are independently of one another by halogen, each optionally substituted by C _l-8 - alkyl, C _l-8 - alkoxy, C _l-8 - alkylamino, di - (C _1-8 - alkyl, Amino, C _1-8 -alkylthio, C _2-5 -alkenylthio, C _2-5 -alkynylthio or C _3-7 -cycloalkylthio, each of which is optionally substituted by halogen, nitro, cyano, C by halogenoalkyl - _l-4 - alkoxy, C _l-4 - halogeno alkoxy, C _1-4 - alkylthio, C _l-4 - halogeno alkylthio, C _l-4 - alkyl, C _l-4 Optionally substituted phenyl, phenoxy or phenylthio,

R ⁶ and R ⁷ are each independently represent hydrogen, respectively optionally substituted by halogen C _l-20 - alkyl, C _l-20 - alkoxy, C _3-8 - alkenyl or C _l-20-alkoxy- Ci _-2O -alkyl; Halogen, Ci _-20 -halogenoalkyl, Ci _-20 -alkyl or Ci _-20 -alkoxy; Or benzyl optionally substituted by halogen, C _{1- 20} -alkyl, C 1- ₂₀ -halogenoalkyl or C _1-20 -alkoxy, or R ⁶ and R ⁷ together are optionally blocked by oxygen or sulfur A compound which exhibits a C _4-6 -alkylene ring,

And compounds of the general formula (I) in stereomerically and enantiomerically pure form.

Particularly preferred compounds of formula (I)

X is C _1-6 - alkyl, halogen, C _l-6 - alkoxy or C _1-2 - represents halogenoalkyl,

Y represents hydrogen, C _1-6 -alkyl, halogen, C _1-6 -alkoxy or C _1-2 -halogenoalkyl,

Z is C _{l-4-alkoxy-alkyl,} halogen or C _1-4

n represents a number of 0 to 2,

Lt; RTI ID = 0.0 > X < / RTI > and Z, together with the phenyl radical to which they are attached,

(Where Y is as defined above) to form a naphthalene radical,

Alkyl sulfonyl, carboxyl, or C0 ^₂ R ₂ - A and B taken together with the bond to which they are tansowonga C _l-5 - alkoxy, C _1-3 - alkylthio, C _1-3 - alkyl sulfonic poksil, C _1-3 Form a saturated or unsaturated 5- to 7-membered ring,

A and B together with the carbon atoms to which they are attached represent a C _{4-7 -triangle} wherein two substituents together with the carbon atoms to which they are attached represent C _{1 -3} -alkyl, C _{1 -3} -alkoxy, fluorine Or a saturated C _5-6 -ring optionally substituted by chlorine and which may be interrupted by oxygen or sulfur,

G is hydrogen (a) or group

Lt; / RTI >

here,

Represents one equivalent of a metal ion or ammonium ion,

L and M represent in each case oxygen or sulfur,

R ¹ is in each case optionally halogen-substituted C _1-16 -alkyl, C _2-16 -alkenyl, C _1-6 -alkoxy-C _1-6 -alkyl, C _1-6 -alkylthio-C _{1 6} - alkyl, C _l-6-alkoxy poly -C _l-6 - alkyl, or a chlorine or C _{l-4-optionally} substituted with alkyl optionally being interrupted by 1 to 2 oxygen and / or sulfur atoms C _3-7 -cycloalkyl; or

Phenyl optionally substituted by halogen, nitro, C _1-4 -alkyl, C _1-4 -alkoxy, C _1-3 -halogenoalkyl or C _1-3 -halogenoalkoxy,

Halogen, C _l-4 - alkyl, C _l-4 - alkoxy, C _l-3 - halogenoalkyl or C _l-3 - by a halogeno alkoxy optionally substituted _phenyl-l -C ₄ -, or represents alkyl,

Furanyl, thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl, each of which is optionally substituted by halogen and / or C _1-6 -alkyl;

Phenoxy-Ci _-5 -alkyl optionally substituted by halogen and / or Ci _-4 -alkyl: or

Pyridyl optionally substituted by alkyl oxy -C _1-5 alkyl, pyrimidyl-oxy -C _l-5 - - alkyl or thiazolyl _oxy-l -C ₅ - alkyl, halogen, amino and / or C _l-4 in each case Lt; / RTI >

R ² is a halogen substituted in each case, C _l-6 - alkyl, C _3-6 - alkenyl, C _1-6 - alkoxy -C _2-6 - alkyl, C _l-6 - poly alkoxy -C _{2- 6} -alkyl,

C _3-7 -cycloalkyl optionally substituted by fluorine, chlorine or C _1-4 -alkyl, or

Each represent phenyl or benzyl, each of which is optionally substituted by halogen, nitro, C _1-4 -alkyl, C _1-3 -alkoxy or C _1-3 -halogenoalkyl,

R ³ , R ⁴ and R ⁵ are each independently of the other C _1-6 -alkyl, C _1-6 -alkoxy, C _1-6 -alkylamino, di- (C _1-6 ) alkyl Amino, C _1-6 -alkylthio, C _3-4 -alkenylthio, C _2-4 -alkynylthio or C _3-6 -cycloalkylthio, or may be substituted by fluorine, chlorine, bromine, no, C _l-3 - alkoxy, C _l-3 - halogeno alkoxy, C _l-3 - alkylthio, C _l-3 - halogenoalkyl alkylthio, C _l-3 - alkyl or C _l-3 - halogenoalkyl Phenyl, phenoxy or phenylthio optionally substituted by alkyl,

R ⁶ and R ⁷ are each independently represent hydrogen, respectively optionally substituted by halogen C _l-20 - alkyl, C _l-20 - alkoxy, C _3-8 - alkenyl or C _l-20-alkoxy- C _l-20 - represents an alkyl or halogen, C _l-5 - halogenoalkyl, C _l-5 - alkyl, C _l-5 - or represents a substituted phenyl optionally substituted by alkoxy, halogen, C _l-5 - alkyl, C _{l-5-halogeno-5-alkyl} or C _l - represents an alkoxy group optionally substituted by benzyl, or R ⁶ and R ⁷ is C _4-6, optionally blocked by an oxygen or sulfur together -alkyl A compound which represents a phenylene group,

And compounds of the general formula (I) in stereomerically and enantiomerically pure form.

Very particularly preferred compounds of formula (I)

X represents methyl, ethyl, propyl, i-propyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,

Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,

Z represents methyl, ethyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy,

n represents 0 or 1,

A and B together with the carbon atom to which they are attached form a C _l-4 - alkoxy, C _l-2 - alkylthio, C _l-2 - alkyl sulfonic poksil, C _l-2 - alkylsulfonyl, carboxyl, or C0 ₂ R ² To form a saturated or unsaturated 5- to 6-membered ring,

A and B together with the carbon atoms to which they are attached represent a C _{4-6 -cycle} wherein two substituents are taken together with the carbon atoms to which they are attached by methyl, ethyl, methoxy, ethoxy, fluorine or chlorine A saturated C _5-6 -ring optionally substituted and interrupted by oxygen or sulfur,

G is hydrogen (a) or group

Lt; / RTI >

here,

Represents one equivalent of a metal ion or ammonium ion,

L and M represent in each case oxygen or sulfur,

R ¹ is in each case optionally fluorine- or chlorine-substituted C _1-14 -alkyl, C _2-14 -alkenyl, C _1-4 -alkoxy-C _1-16 -alkyl, C _1-4 -alkyl thio -C _l-6 - alkyl, C _l-4 - poly alkoxy -C _l-4 - alkyl, or fluorine, chlorine, optionally substituted by methyl or ethyl, 1 to 2 oxygen and / or interrupted by a sulfur atom C _3-6 -cycloalkyl which may be substituted,

Is phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or nitro, Or phenyl-C _1-3 -alkyl optionally substituted by ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,

Thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,

C _1-4 -alkyl optionally substituted by fluorine, chlorine, methyl or ethyl,

If the or each by a fluorine, chlorine, amino, methyl or ethyl optionally substituted _pyridyloxy-l -C ₄ - alkyl, _{pyrimidyl-oxy-l} -C ₄ - alkyl or thiazolyl _oxy-l -C ₄ - alkyl, Lt; / RTI >

R ² is a fluorine or chlorine by an in each case optionally substituted C _1-14 - alkyl, C _3-14 - alkenyl, C _1-4 - alkoxy -C _2-6 - alkyl, C _l-4 - poly alkoxy -C _2-6 -alkyl,

Represents C _3-6 -cycloalkyl optionally substituted by fluorine, chlorine, methyl or ethyl, or

Each independently represent phenyl or benzyl optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl;

R ^3, R ⁴ and R ⁵ are each other by each of the fluorine or chlorine independently optionally substituted C _l-4 - alkyl, C _l-4 - alkoxy, C _l-4 - alkylamino, di - (C _l-4 -alkyl) amino or C _l-4 - represent alkylthio or, respectively, fluorine, chlorine, bromine, nitro, cyano, C _l-2-alkoxy, C _{l-4-fluoro-alkoxy,} C _l-2-chloro alkoxy, C _l-2 - alkylthio, C _l-2 - fluoro-alkylthio, C _l-2 - chloro-alkylthio or C _l-3 - represents a phenyl, phenoxy or phenylthio optionally substituted by alkyl, optionally,

R ⁶ and R ^7, independently of each other represents hydrogen or fluorine, respectively, by a chlorine or bromine, optionally substituted C _l-l0 - alkyl, C _3-6 - alkenyl, C _l-l0 - alkoxy or C _l-l0 -alkoxy -C _1-l0 - represents an alkyl or fluorine, chlorine, bromine, C _l-2 - halogenoalkyl, C _l-2-alkyl or C _l-4 - or represents a phenyl optionally substituted by alkoxy , fluorine, chlorine, bromine, C _l-4-a with an alkoxy represents an optionally substituted benzyl, or together are oxygen or by sulfur, optionally block - alkyl, C _{l-4-halogeno-C 1-4} alkyl, or A compound which represents a C _4-6 -alkylene ring,

And compounds of the general formula (I) in stereomerically and enantiomerically pure form.

In addition to the compounds mentioned in the preparation examples, 3-aryl-4-hydroxy-isoquinolines of general formula (Ia) - dihydrofuranone derivatives are shown below.

Table 1

The following 3-aryl-4-hydroxy- -dihydrofuranone derivatives of formula (Ib) may be mentioned individually in addition to the compounds mentioned in the preparation examples:

The following 3-aryl-4-hydroxy- -dihydrofuranone derivatives of the formula (Ic) may be mentioned separately in the compounds mentioned in the preparation examples:

Table 3

In addition to the compounds mentioned in the preparation examples, 3-aryl-4-hydroxy- - < / RTI > dihydrofuranone derivatives, respectively.

Table 4

When using ethyl 1- (2,6-dichlorophenylacetyloxy) -4-isopropoxy-cyclohexanecarboxylate according to method (A), the process of the process according to the invention can be represented by the following formula:

According to process (B) (variant a), 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (2- ethoxy) pentamethylene- -Dihydrofuran-2-one and pivaloyl chloride as starting materials, the process of the reaction according to the invention can be represented by the following formula:

According to method (B) (variant?) 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (2- methoxy) tetramethylene- - dihydrofuran-2-one and acetic anhydride as starting materials, the process of the reaction according to the invention can be represented by the following formula:

According to method (C), 3- (2,4-dichlorophenyl) -4-hydroxy-5, 5- (3-propoxy) pentamethylene- -Dihydrofuran-2-one and ethoxyethyl chloroformate as starting materials, the process of the reaction according to the invention can be represented by the following formula:

According to the method (D?), 3- (2,4,6-trimethylphenyl) -3-hydroxy-5,5- (3-tert-butoxy) pentamethylene- -Dihydrofuran-2-one and methyl chloroformate as starting materials, the process of the reaction according to the invention can be represented as follows.

According to method (E), 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (1,2- tetramethylene) trimethylene- - dihydrofuran-2-one and methanesulfonyl chloride as starting materials, the process of the reaction according to the invention can be represented by the following formula:

According to method (F), 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (1,4- -Dihydrofuran-2-one and 2,2,2-trifluoromethylmethanechlorothiophosphate are used as starting materials, the reaction procedure can be represented by the following formula.

According to the method (G _alpha ), 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (2,3- tetramethylene) tetramethylene- - dihydrofuran-2-one and ethyl isocyanate are used as starting materials, the reaction procedure can be represented by the following formula:

According to the method (G _β ), 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (2-methylmercapto) pentamethylene- -Dihydrofuran-2-one and dimethylcarbamoyl chloride are used as starting materials, the reaction process can be represented by the following formula.

According to Method H, 3- (2,4,6-trimethylphenyl) -4-hydroxy-5,5- (2-methoxy) pentamethylene- - dihydrofuran-2-one and NaOH are used as reactants, the process of the reaction according to the invention can be represented by the following formula:

The compound of the formula (II) required as a starting material in the above reaction (A) is novel but can be prepared by a simple method in principle by a known method.

In this formula,

A, B, X, Y, Z, n and R ⁸ have the above-mentioned meanings.

For example, the 0-acyl- alpha -hydroxycarboxylic acid ester of formula (II)

a) acylating with a phenylacetyl halide of the formula (XIV) for a 2-hydroxycarboxylic acid (ester) of the formula (XIII) and optionally esterifying or hydroxycarboxylic acid of the formula (IIa) Esterified [Chem. Ind. (London) 1568 (1968).

In this formula,

A, B, X, Y, Z and n have the abovementioned meaning,

R ¹² represents hydrogen (XIIIa) or alkyl (XIIIb)

Hal represents chlorine or fluorine.

The compound of formula (IIa) can be obtained, for example, from a phenylacetyl halide of formula (XIII) and a hydroxycarboxylic acid of formula (XIIIa) (Chem. Reviews 52 237-416 (1953)].

As examples of the compound of the formula (II), the following compounds may be mentioned.

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2-chlorophenyl-6-fluorophenyl-acetyloxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-acetoxy) -2-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-lacetoxy) -3-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-acetoxy) -4-methoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-acetoxy) -4-ethoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-acetoxy) -4-isopropoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-acetoxy) -4-t-butoxy-cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -3,4-trimethylene-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -3,4-trimethylene-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -3,4-trimethylene- cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -3,4-trimethylene-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -3,4-trimethylene-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -3,4-trimethylene-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluorophenylphenyl-acetoxy) -3,4-trimethylene- cyclohexanecarboxylate

Ethyl 1- (2,4-dichlorophenyl-acetyloxy) -2,5-methylene-cyclohexanecarboxylate

Ethyl 1- (2,6-dichlorophenyl-acetyloxy) -2,5-methylene-cyclohexanecarboxylate

Ethyl 1- (2-chloro-6-fluorophenyl-acetyloxy) -2,5-methylene- cyclohexanecarboxylate

Ethyl 1- (2,4-dimethylphenyl-acetyloxy) -2,5-methylene-cyclohexanecarboxylate

Ethyl 1- (2,6-dimethylphenyl-acetyloxy) -2,5-methylene-cyclohexanecarboxylate

Ethyl 1- (2,4,6-trimethylphenyl-acetoxy) -2,5-methylene-cyclohexanecarboxylate

Ethyl 1- (2,6-dichloro-4-trifluoromethylphenyl-acetoxy) -2,5-methylene- cyclohexanecarboxylate

The method (A) can be carried out by carrying out an intramolecular condensation reaction in the presence of a base for a compound of the general formula (II) (wherein A, B, X, Y, Z, n and R ⁸ have the above- .

The diluents which can be used in the process (A) according to the invention are all inert organic solvents. These include preferably hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, dimethylsulfoxide, sulfolane, dimethylformamide and N-methyl Polar solvents such as pyrrolidone and also alcohols such as methanol, ethanol, propanol, isopropanol, butanol, iso-butanol and t-butanol can be used.

The bases (deprotonating agents) which can be used to carry out the process (A) according to the invention are all conventional proton acceptors. These include preferably alkali metal oxides such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides and alkaline earth metal carbonates Can be used, all of which can also be used, for example, with triethylbenzylammonium chloride, tetrabutylammonium bromide, adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris- Ethoxyethyl) amine). ≪ / RTI > Alkali metals such as sodium or potassium may also be used. In addition, alkali metal amides such as sodium amide, sodium hydride and calcium hydride, alkali metal hydrides, alkaline earth metal amides and alkaline earth metal hydrides, and alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium t- May also be used.

In carrying out the process (A) according to the invention, the reaction temperature can be varied within a wide range. Generally, the reaction is carried out at a temperature of from 0 to 250 캜, preferably from 50 to 150 캜.

The process (A) according to the invention is generally carried out under atmospheric pressure.

In carrying out the process (A) according to the invention, the reactants of the general formula (II) and the deprotonated bases are generally used in approximately twice the equimolar amount. However, it is possible to use a large amount (not more than 3 mol) of one component or the other components.

The process (B?) Is characterized in that a compound of formula (Ia) is reacted with a carbonyl halide of formula (III).

When an acid halide is used, the diluent which can be used in the process (B?) According to the invention is any solvent which is inert to these compounds. These include preferably hydrocarbons such as benzene, benzene, toluene, xylene and tetralin, halogeno hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ketones such as acetone and methyl isopropyl ketone , Ethers such as diethyl ether, tetrahydrofuran and dioxane, further carboxylates such as ethyl acetate, and also strong polar solvents such as dimethyl sulfoxide and sulfolane can be used. The acid halide is sufficiently soluble for hydrolysis If stable, the reaction can also be carried out in the presence of water.

When using the corresponding carbonyl halides, the acid binders suitable for the reaction of the process (B?) According to the invention are all customary acid acceptors. These include preferably triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig's base and N, N-dimethylaniline , Alkaline earth metal oxides such as magnesium oxide and calcium oxide, alkali metal carbonates and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used .

In the process (B?) According to the invention, and also when a carboxylic acid halide is used, the reaction temperature can be varied within a wide range. In general, the reaction is carried out at a temperature of from -20 to + 150 ° C, preferably from 0 to 100 ° C.

In carrying out the process (B?) According to the invention, the starting materials of the general formula (Ia) and the carboxylic acid halides of the general formula (III) are generally used in approximately equivalent amounts. However, it is also possible to use a large excess (less than 5 moles) of the carboxylic acid halide. The post-treatment is carried out in a conventional manner.

The process (Bβ) is characterized by reacting a compound of the formula (Ia) with a carboxylic acid anhydride of the formula (IV).

In the case of using the carboxylic acid anhydride as a reactant of the general formula (IV) in the process (B?) According to the invention, the diluent which can preferably be used is a diluent suitable when an acid halide is used. Separately, the excess carboxylic acid anhydride also acts simultaneously as a diluent.

In carrying out the process (B?) According to the invention, the reaction temperature can also be varied within a wide range when using carboxylic acid anhydrides. In general, the reaction is carried out at a temperature of from -20 to + 150 ° C, preferably from 0 to 100 ° C.

In carrying out the process (Bβ) according to the invention, the starting materials of the general formula (Ia) and the carboxylic anhydrides of the general formula (IV) are generally used in approximately equivalent amounts. However, it is also possible to use a large excess (5 moles or less) of the carboxylic acid halide. The post-treatment is carried out in a conventional manner.

Generally, the resulting carboxylic acid as well as the diluent and excess carboxylic acid anhydride are removed by distillation or by washing with an organic solvent or water.

Process (C) is characterized by reacting a compound of formula (Ia) with a chloroformic ester or chloroformic thioester of formula (V).

When using the corresponding chloroformic or chloroformic thioesters, the acid binders suitable for the reaction of process (C) according to the invention are all conventional acid acceptors. These are preferably tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Huing base and N, N-dimethylaniline, alkaline earth metal oxides such as magnesium oxide and calcium oxide, Alkali metal carbonates such as potassium carbonate and calcium carbonate and alkaline earth metal carbonates, and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used.

When using chloroformic acid esters or chloroformic acid thioesters, the diluents which can be used in process (C) according to the invention are all solvents which are inert to these compounds. These include preferably hydrocarbons such as benzene, benzene, toluene, xylene and tetralin, halogeno hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ketones such as acetone and methyl isopropyl ketone Ethers such as diethyl ether, tetrahydrofuran and dioxane, further carboxylates such as ethyl acetate, and also strong polar solvents such as dimethyl sulfoxide and sulfolane can be used.

When a chloroformic acid ester or a chloroformic acid thioester is used as a carboxylic acid derivative of the formula (V), the reaction temperature for carrying out the process (C) according to the invention can be varied within a wide range. When the reaction is carried out in the presence of a diluent and an acid binder, the reaction temperature is generally -20 to +100 DEG C, preferably 0 to 50 DEG C.

The process (C) according to the invention is generally carried out under atmospheric pressure.

In carrying out the process (C) according to the invention, the starting materials of the general formula (Ia) and generally approximately equivalent amounts are used. However, it is also possible to use a large amount (not more than 2 mol) of one component or other components. The post-treatment is then carried out in a conventional manner. Generally, the precipitated salts are removed and the remaining reaction mixture is concentrated by stripping the diluent.

In the production method (D), about 1 mol of a chloromonothioformic acid ester of the formula (VI) or chlorodithioformic acid (1) at 0 to 120 째 C, preferably 20 to 60 째 C per 1 mol of the starting compound of the formula (Ia) The ester is reacted.

Suitable diluents which are optionally added are all inert polar organic solvents such as ethers, amides, sulfones and sulfoxides.

Dimethyl sulfoxide, tetrahydrofuran, dimethyl formamide, and dimethyl sulfide are used.

In a preferred embodiment, when an enolate salt of general formula (Ia) is prepared by addition of a steel deprotonation agent such as, for example, sodium hydride or potassium tert-butylate, no acid-binder may be added .

In the case of using acid binders, suitable materials are conventional inorganic or organic bases, examples of which are sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction can be carried out under atmospheric pressure or elevated pressure, preferably under atmospheric pressure. The post-treatment is carried out by a conventional method.

In the production process (E), about 1 mole of the sulfonyl chloride (VII) of the formula (VII) is used per 1 mole of the starting material of the formula (Ia). The process is preferably carried out at a temperature of from 0 to 150 캜, and in particular from 20 to 70 캜.

Suitable diluents which are optionally added are all inert polar organic solvents such as ethers, amides, nitriles, alcohols, sulfones and sulfoxides.

Dimethyl sulfoxide, tetrahydrofuran, dimethyl formamide and dimethyl sulfide are preferably used.

In a preferred embodiment, when an enolate salt of general formula (Ia) is prepared by addition of a steel deprotonation agent such as, for example, sodium hydride or potassium tert-butylate, no acid-binder may be added .

In the case of using acid binders, suitable materials are conventional inorganic or organic bases, examples of which are sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction can be carried out under atmospheric pressure or elevated pressure, preferably under atmospheric pressure. The post-treatment is carried out by a conventional method.

When the compound of formula (Ie) is obtained in the production process (F), 1 to 2 moles, preferably 1 to 2 moles, of the compound of the formula (Ia) is added at a temperature of -40 to 150 ° C, preferably -10 to 110 ° C, 1 to 1.3 mol of the phosphorus compound of the formula (VIII) is reacted.

Suitable diluents which are optionally added are all inert polar organic solvents such as ethers, amides, nitriles, alcohols, sulfides, sulfones, sulfoxides and the like.

Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide and methylene chloride are preferably used.

Suitable acid binders which are optionally added are conventional inorganic or organic bases such as hydroxides or carbonates. Examples thereof include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction can be carried out under atmospheric pressure or elevated pressure, preferably under atmospheric pressure. Post treatment is carried out by a conventional method of organic chemistry.

The final product obtained is preferably purified by crystallization, chromatographic purification or so-called " incipient distillation ", i.e. removal of volatile components in vacuo.

In the production process (Ga), about 1 mole of the isocyanate of the general formula (IX) per mole of the starting compound of the general formula (Ia) is reacted at a temperature of 0 to 100 캜, preferably 20 to 50 캜.

Suitable diluents which are optionally added are all inert organic solvents such as ethers, amides, nitriles, sulfones or sulfoxides.

If appropriate, a catalyst may be added to accelerate the reaction rate. Catalysts that can be used very advantageously are organotin compounds such as, for example, dibutyltin dilaurate. The reaction is preferably carried out under atmospheric pressure.

In the production process (G?), The carbamoyl chloride or thiocarbamoyl chloride of the formula (X) is reacted with about 1 mole of the starting compound of the formula (Ia) at 0 to 150 ° C, preferably 20 to 70 ° C, .

Suitable diluents which are optionally added are all inert polar organic solvents such as ether, amide, sulfone or sulfoxide.

Dimethylsulfoxide, tetrahydrofuran, dimethylformamide or dimethylsulfide is preferably used.

In a preferred embodiment, when an enolate salt of general formula (Ia) is prepared by addition of a steel deprotonation agent such as, for example, sodium hydride or potassium tert-butylate, no acid-binder may be added .

When an acid binder is used, suitable materials are conventional inorganic or organic bases, examples of which may include sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.

The reaction can be carried out under atmospheric pressure or elevated pressure, preferably under atmospheric pressure. The post-treatment is carried out by a conventional method.

Process (H) is characterized in that the compound of formula (Ia) is reacted with metal hydroxide (XI) or amine (XII).

The diluent that can be used in the present invention can preferably be an ether such as tetrahydrofuran, dioxane, diethyl ether, or an alcohol such as methanol, ethanol or isopropanol, and water. Process (H) Is generally performed under atmospheric pressure. The reaction temperature is generally -20 to 100 占 폚, preferably 0 to 50 占 폚.

In carrying out the process (H) according to the invention, about equimolar amounts of the starting materials of the formulas (Ia) and (XII) or (XII) are used. However, it is possible to use a large amount (not more than 2 mol) of one component or other components.

The compounds of formula (I) according to the invention can be used for controlling harmful organisms. Hazardous organisms are unwanted animal pests, especially insects, mites and nematodes, harmful to plants or higher animals. However, harmful organisms also include unwanted plants.

The active compounds of the invention are suitable for the rescue of animal pests, preferably arthropods and nematodes, especially insects, mites and nematodes emerging in the field of agriculture, forestry, storage and materials, and hygiene. They are active against normally susceptible and resistant species and all or part of the growing season. The above-mentioned harmful organisms include the following.

Isopoda, for example Oniscus asellus, Armadillidium vulgare, and Porcellio scaber.

A diplopoda neck, for example, Blaniulus guttulatus.

Chilopoda neck, for example, Geophilus carpophagus and Scutigera spec.

A neck of Symphyla, for example, Scutigerella immaculata.

Thysanura neck, for example, Lepisma saccharina.

Collembola neck, for example Onychiurus armatus.

Orthoptera sp., Such as Blatta orientalis, Periplaneta americana, Leucophaeamaderae, Blattella germanica, But are not limited to, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, and Schistoser < RTI ID = 0.0 > Schistocerca gregaria.

Dermaptera tree, for example Forficula auricularia.

Isoptera, for example, Reticulitermes spp.

Anoplura species such as Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. And Linognathus spp.

Mallophaga necks, for example Trichodectes spp. And Damalinea spp.

Thysanoptera species, for example, Hercino thrips femoralis and Thrips tabaci.

Heteroptera species such as Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, rodent, Rhodnius prolixus and Triatoma spp.

For example Homoptera sp., Such as Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, The strains of Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundi, (Hyalopterus arundinis), Macrosiph-um avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp. Spp.), Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelaxstria, Telos (Laodelphax striatellus), Nilapar Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp., And the like. .

Lepidoptera species such as Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Lactobacillus spp. For example, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. , Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., And the like. Such as Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodinia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chyloides spp. Chi-lo spp., Pyrausta nubilalis, Ephe-stia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, and Cacoecia podana. Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, and Tortrix viridana.

Coleoptera species, for example Anobium punctatum, Rhizopertha dominica. But are not limited to, Bruchidus obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa deceminala For example, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epi-lachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, ), Cosmopolites sordidus, Ceuthorrhynchus assi-milis. Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Rick < RTI ID = 0.0 > Lyctus spp., Meligethes ae-neus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, But are not limited to, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.

Hymenopera sp., Such as Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. Vespa spp.).

Diptera spp., For example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca subsp. Musca spp., Fannia spp., Calliphora erythrocephala, Luci1ia spp., Chrysomia spp., Cuterebra spp. , Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Taba spp. Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia spp., Tetanus spp. hyoscyami, Ceratitis capitata, Dacus oleae, and T-palaparudose (T ipula paludosa).

Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.

Arachnida species, for example, Scorpio maurus and Latrodectus mactans.

Acarina necks, such as Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophis ribis, Such as Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp. ), Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Tarsonemus spp. , Bryobia praetiosa, Panonychus spp. And Tetranychus spp.).

Examples of plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp. (Heterodera spp.), Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema app., And tricodorus subsp. (Trichodorus spp.).

In addition, the active compounds of the general formula (I) according to the invention also exhibit excellent fungicidal activity and can be used, for example, for the control of plant diseases such as rice blast fungus (Picholaria).

The active compounds according to the present invention can be used as commercial products as a mixture with other active compounds such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides, Can be in use. Insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and materials produced by microorganisms.

The active compounds according to the invention may also be present in the form of a commercial formulation as a mixture with a synergistic agent and a working form prepared from these preparations. A synergist is a compound that increases the action of an active compound but does not need to be added in order to manifest itself.

The active compound content in the dosage form prepared from a commercial formulation can be varied within a wide range. The active compound concentration in the mold may be 0.0000001 to 95% by weight, preferably 0.0001 to 1% by weight.

They are used in a conventional manner suitable for the type of use.

The compounds according to the invention are also particularly suitable for the treatment of, for example, crops, corn, vegetables, etc., or of growth and breeding materials such as bulbs,

Hygiene Hazardous Biological and Storage Products When used against harmful organisms, the active compounds exhibit excellent residual activity against wood and clay and exhibit excellent stability to alkalis on scouring materials.

The active compounds according to the present invention can be used as leaves, desiccants, leaf plant killing agents and, in particular, weed killers. The weed, in a broad sense, whether it acts as an unwanted or selective herbicide depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants.

However, the use of the active compounds according to the invention is not limited to these, and extends to other plants in the same way.

The compounds of the present invention are suitable for the overall control of weeds on sidewalks and squares, for example on industrial sites and railroads, and on planted or unplanted trees, depending on the concentration. Likewise, the compounds of the present invention may be used in planting, planting, orchard, vineyard, citrus orchard, nuts orchard, banana plantation, coffee plantation, tea plantation, rubber plantation, coconut plantation, cocoa plantation, Can be used to control weeds in perennial crops growing on the lawn, turf and grassland and for the selective control of weeds in annual crops.

The active compounds according to the invention are particularly suitable for the selective control of terminal weeds among dicotyledonous crops by pre- and post-germination methods. The active compounds of the present invention can be used particularly successfully in controlling weeds in cotton or beet.

The active compounds according to the invention can be used as weeds control itself or in combination with known herbicides in the form of their preparations, in the form of finished preparations or tank mixes.

Suitable herbicides as mixtures include, for example, anilides, such as diflufenicane and propanil; Arylcarboxylic acids such as dichloropicolinic acid, dicamba and picloram: aryloxyalkanoic acids such as 2,4 D, 2,4 DB, 2,4 DP, fluroxipyr, MCPA, MCPP and trichloro Pyre; Acyloxy-phenoxy-acanoic acid esters such as diclofol-methyl, phenoxyphospholyl-ethyl, fluazifbutyl, halvcipiter-methyl and quinizalofol-ethyl; Azinones such as chloridazone and norplazone; Carbamates such as chlorpropam, desmedipham, penmedipam and pro-pal; Chloroacetanilides such as alachlor, racetchlor, butachlor, metazachlor, metolachlor, pretillachlor and propanol; Dinitroanilines such as dicalazine, pendimethalin and trifluralin; Diphenyl ethers such as acifluorfen, bifenox, fluoro lycopene, pomesapen, halosapene, lactone pen, and oxyfluorfen: urea such as chlorotoluron, diuron, fluorometuron, isoprofen, Turon, Linalool and Metabenzthiazuron; Hydroxyamines such as alloxydim, clethodim, cycloxydim, cetoxydim, and tralcoximid; Imidazolidinones such as imazetapyr, imazamethabenz, imazapyr and imazacquin; Nitriles such as bromocinninyl, dicarbonyl and dioxinyl; Oxyacetamides such as mepenacet; But are not limited to, benzenesulfuron-methyl, chloromuron-ethyl, chlorersulfuron, cynosulfuron, methosulfuron-methyl, nicosulfuron, pyrimisulfuron, pyrazosulfuron- Benzuron-methyl; Thiocarbamates, such as butyrate, cyclohexylate, dialkate, EPTC, espeb, molinate, prosulfocop, thiobenzoc and tri-alate; Triazines such as atrazine, cyanazine, simajin, simethrin, terbutrine and tbutyl azine; Tri-majinone, such as hexazinone, metamitron, mettriazine; Other examples include, but are not limited to, aminotriazole, benzpresate, benzazone, neomethyline, clomazone, clopyralide, diphenocquat, dithiopyr, etupsemate, fluorochloride, gluposinate, glyphosphate , Isosbene, pyridate, quinclorac, queen mecak, sulfosate and tridiphenyl.

Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, algicides, plant nutrients and soil condition improvers are also possible.

As pesticides, the following can be mentioned.

But are not limited to, arginine, arginin, arginin, arginin, arginine, alpha methine, betacyclutrin, berfenentin, bulopentrox, But are not limited to, methine, esfenvalerate, etofenprox, penproperrin, penvalerate, flucentrinate, pullulvalinate, lambda-cyhalothrin, permethrin, pelethmethrin, pelerthrum, ≪ / RTI > ophen, tralomethrin, zetamethrin,

But are not limited to, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene But are not limited to, wheat, flouricap, propecab, propoxur, derbum, thiodicab, thiopanox, trimethacop, XMC, xylic acid, Methylene, demethone S, diazinon, dichlorobenzene, diazonium, dibromide, and the like. Dithiothreitol, dimethoate, dimethylphosphate, dioxathione, disulfotone, edifenphos, etion, etrimphose, penitrothion, pention, isosapphos, Formothion, heptonofos, iprovenphose, diazophos, isoxathion, folate, malathion, mercaban, lerubinphose, resulfone , Methacryphose, metamidocose, naldehyde, omeitoate, oxydemethone M, oxydepropos, parathion A, parathion M, petiole, phorate, phosphoryl, phosphat, And a pharmaceutically acceptable carrier such as a microsphere, a microsphere, a microsphere A, a microsphere A, a microsphere A, a microsphere A, a microsphere A, a microsphere A, a microsphere A, Dimethylthi [5-methoxy-1,3,4-thiadiazole-2 (3H) -triazole, thiomethan, thiazin, trichlorfon, triazophos, (3-methyldithiophosphate), DDVP (dimethyl 2,2-dichlorovinyl phosphate), CYAP (0,0-dimethyl 0-4-cyanophenylthiophosphate)

Buproprapine, chlorofluorescent, hexaflumuron, pyriproxifen, tebufenozide, teflubenzuron, triflumuron,

(NI-25), N-methyl-3-pyrrolidone, N-methyl-N'-

But are not limited to, amoxicillin, abamectin, amitrazine, avermectin, azadirachin, benzyltepth, bacillus trinjisensis, chylomagazine, diapenturon, emamectin, etofenprox, fenprud, fipronil, But are not limited to, thiourea, nulone, methaldehyde, milbemectin, pimetrozine, tbufenpyrad, triazuron, aldiacob, bendiocab, bendiocab, benfuracab, carbofuran, carbosulfan, chlorethoxyphos, Phthalocyanine, furathiocob, HCH, diazopos, isophenphos, methiocop, monocrotophos, nifentipram, oxa, phthalocyanine, phthalocyanine, But are not limited to, wheat, phorate, peppermint, prothiophos, pyraclucose, cefthus, zeaxanth, proteothiose, pyraclucose, cefoxilafluofen, tebuflimymph, tefluthrin, Thia Penx,

But are not limited to, azocyclotin, butylpyridene, chloropentazine, cyclohexatin, dipentaurone, diethion, emamectin, phenazakin, penbutatin oxide, phenothiopaque, penproparathine, But are not limited to, fluconazole, fluconazole, flucuron, flucycloxirone, fluphenoxuron, fluvolinate, spearpox, Heccians, ibemectin, methidathion, monocrothophos, moxidetin, (4-chlorophenyl) -1- (ethoxymethyl) -5 (4-fluorophenyl) - (trifluoromethyl) -lH-pyrrole-3-carbonitrile (AC 303630),

Dicotol, chlorobenzilate, bromopropylate, clofenone, BPPS.

Particularly useful mixing partners also include, for example:

Fungicide:

2-aminobutane; Methyl-6-cyclopropyl-pyrimidine: 2 ', 6'-Dibromo-2-methyl-4'-trifluoromethoxy- -Thiazole-5-carboxyanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) -acetamide; 8-hydroxyquinoline sulfate; Methyl (E) -methoximino-methyl (E) -2- (2- [6- (2-cyanophenoxy) -pyrimidin- [Alpha] - (o-tolyloxy) -octolyl] acetate, 2-phenylphenol (OPP, aldimorph, amipropos, anilazine, azaconazole, benzalacyl, benodanil, But are not limited to, biphenyl, bitterol, blasticidin-5, bromuconazole, bupirimate, butothioate, calcium polysulfide, , Chloropenes, chloropycins, chlorothalonyls, czulolinate, coupura neps, sisopanil, cyproconazole, cyprofuran,

But are not limited to, dichloropropene, dichlorobutene, dichlorobutene, dichlorobutazole, dichlorobutazole, dichlorofuranide, dichloromethane, dichlororan, diethophenoxy, difenoconazole, dimethyimol, dimethomorph, dimiconazole, , Diphenylamine, dipyrithione, ditalaphosphate, dithianone, dodine, dreyolane solanone, ediphenose, epoxiconazole, ethidimol, etidiazole, phenamarox, penuborazone, But are not limited to, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, , Flutolamide, flutolanil, flutriapol, polyphet, fosetyl-aluminum, phthalide, faperidazole, furaloxil, furerecylox, guazatine,

But are not limited to, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imbeconazole, iminostadine, ibuprofen (IBP), iprodione,

Copper nitrate, copper formate, copper formate, copper hydroxide, copper naphthalate, copper oxychloride, copper sulfate, copper dioxide, oxine-copper and borideaux mixture, mancofer, mancoffee, maneb, But are not limited to, methionine, methionine, methanone, methionine, methanone, methanone, methanone,

Nickel, dimethyldithiocarbamate, nitrotal-isopropyl, norarimol,

Oxalic acid, oxalic acid, oxalic acid, oxalic acid,

But are not limited to, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, Naphthol, propinep, pyrazole, pyrimethoxyl, pyrimethanil, pyroquilon,

Methylene, thiam, tolclofos-methyl, tolyl fl uorine (PCNB), sulfur and sulfur preparations, tebuconazole, teclofhthalam, technazen, tetraconazole, thiabendazole, thiophene, Triamcinol, triamcinol, triacylglycerol, triamcinol, triacylglycerol, tridermorph, triflumizole, triphlorin, trithiocinazole, validamycin A, .

disinfectant:

Hydroxypentyl, nickel dimethyldithiocarbamate, carysuccinic acid, octylinone, furancarboxylic acid, oxytetracycline, provenazole, streptomycin, teclophthalamide, copper sulfate and other copper preparations.

The active compounds may be used as such or in the form of a preparation prepared by dilution therefrom, or in the form of their preparation, such as solutions, suspensions, emulsions, powders, powders, pastes and granules. They are used in conventional manner, for example by conventional methods such as watering, spraying, dispersing or dispersing.

The active compounds according to the invention can be applied either before or after germination of the plants.

They may also be blended into the soil before sowing.

The amount of active compound can be varied within a considerable range. This is inherently dependent on the nature of the desired effect. Generally, the active compound is used in an amount of 0.01 to 10 kg, preferably 0.05 to 5 kg, per hectare of the soil surface.

For the production of pesticides, the active compounds according to the invention may be formulated in the form of customary preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active compounds, seeds And can be converted to formulations for use with combustion devices such as fumigant cartridges, fumigation cans, fumed coils, etc., and ULV antifreeze agents and on-off agents, such as customary agents such as ultrafine capsules in polymeric materials and coating compositions.

The active compounds according to the present invention can be used in the form of solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active compounds, Conventional formulations such as microcapsules in coating compositions, formulations for use with combustion devices such as fumigation cartridges, fumigation cans, coils, etc., and ULV antifreeze and on-offs.

These preparations can be prepared in a known manner, for example by mixing the active compound with an extender, i. E. A liquid solvent, a pressurized liquefied gas and / or a solid carrier, using a surfactant, i. E. An emulsifier and / or a dispersant and / or a foam- . When water is used as the weight agent, for example, an organic solvent can also be used as an auxiliary solvent. Liquid-phase solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic compounds such as chlorobenzene, chloroethylene or methylene chloride, and chlorinated aliphatic hydrocarbons, cyclohexane or paraffins, for example aliphatic hydrocarbons such as mineral oil fractions , Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethyl formamide and dimethyl sulfoxide and water are suitable. A liquefied gas weight agent or carrier means an aerosol propellant such as a liquid such as a halogenated hydrocarbon, butane, propane, nitrogen and carbon dioxide, which is gaseous at ambient temperature and atmospheric pressure.

Solid carriers include, for example, ground natural minerals such as kaolin, clay, talc, chalk, quartz, Atta pulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silicas, alumina and silicates Fit; Solid carriers for granules include, for example, ground and crushed natural ores such as calcite, marble, pumice, hemastone and dolomite, synthetic granules of inorganic and organic powders, and organic materials such as sawdust, coconut shells, cornstalks and tobacco stalks Of granules are suitable; Emulsifiers and / or foam-formers include nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulphates, aryl sulphonates and Albumin hydrolysis products are suitable, and as the dispersing agent, for example, lignin-sulfite waste liquid and methyl cellulose are suitable.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions such as gum arabic, polyvinyl alcohol and polyvinyl acetate, phospholipids such as cephalin and lecithin, and synthetic phospholipids can be used in the formulations. As other additives, mineral oil and vegetable oil can be used.

For example, inorganic pigments such as iron oxide, titanium oxide and prussian blue and colorants such as organic dyes for alizarin dyes, azo dyes and metal phthalocyanine dyes and salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc The same micronutrients can be used.

The preparations generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active compound.

The active compounds according to the invention are insecticides, attractants, sterilants, acaricides, nematocides, fungicides. As a mixture with other active compounds such as growth-regulating substances or herbicides, as well as in the use forms prepared from these preparations. Insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and materials produced by microorganisms.

The composition according to the invention may also contain at least one compound of formula (I) and, where appropriate, customary extenders and auxiliaries, at least one surfactant.

The process for the preparation of the compound of formula (I) according to the invention is illustrated by the following preparative examples and biological activity is described by the following biological example.

The compounds shown below are compounds to be used as comparative substances in the application examples.

(All of which are described in EP 0,528,146)

Example A

Heliothis virescens test

Solvent: Dimethylpolonamide 7 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

One part by weight of the active compound is mixed with the above amount of the solvent and the emulsifier, and the concentrate is diluted with water to the desired concentration to prepare a suitable preparation of the active compound.

Soybean sprouts (glycine max: Glycine max) are treated by soaking in the active compound preparation at the desired concentration and infected with tobacco budworm larvae (Heliothis virescens) while the leaves are moist.

After a certain period of time has elapsed, the percentage of relief is determined. 100% means that all mustard tobacco budworm larvae have been killed, and 0% means that not more than one mustard tobacco budworm larvae have died.

In this test, for example, the compounds of Preparative Examples (Ib-6), (Ib-8), (Ic-4) and (Ic-5) While the prior art compounds showed less than 40% remission rate.

Example B

Myzus Exam

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration to produce the appropriate preparation of the active compound.

Cabbage leaves (Brassica oleracea) are treated by immersion in the active compound preparation at the desired concentration and infected with peach aphid (Myzus persicae) while the leaves are moist.

After a certain period of time has elapsed, the percentage of relief is determined. 100% means that all cabbage moth caterpillars have been killed, and 0% means that not one peach aphid has been killed.

In this test, for example, the preparations of Examples (Ic-4) and (Ic-5) showed recovery rates of 85% or more after 6 days at a concentration of 0.01%.

Example C

Critical concentration test / muscle-penetration

Test insect: Phaedon cochleariae larvae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the abovementioned amount of solvent, the amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration to prepare a suitable preparation of the active ingredient.

The active compound preparation is uniformly mixed with the soil. The concentration of active compound in the formulation is practically unimportant and the weight of the active compound per unit of soil given in ppm (mg / l) is critical. The treated soil is transferred to a pot and cabbage (Brassica oleracea) is planted there. The active compound can be absorbed from the soil by the roots of the plant and transferred to the leaves in this manner.

To measure the muscle-penetrating effect, the leaves are infected to the test animals described above after 7 days. After an additional two days, the dead animals are counted or observed for evaluation. The muscle-penetrating action of the active compound is deduced from the remedial value. It is 100% when all test animals are killed and 0% when many test insects are still alive, as in the untreated control group.

In this test, the preparation example (Ic-4) exhibited a 100% relief rate at an active compound concentration of 20 ppm.

Example D

Tetranychus test (OP resistance)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: alkylaryl polyglycol ether 1 part by weight

1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier and the resulting concentrate is diluted with water to the desired concentration to prepare a suitable preparation of the active compound.

Soybean plants (Phaseolus vulgaris) are soaked in the active compound preparation at the desired concentration and infected with this spotted spider mite (Tetranychus urticae) at the developmental stage while the plants are damp.

After a certain period of time has elapsed, the percentage of relief is determined. 100% means that all spider mite has been killed, and 0% means that no spider mite has been killed.

In this test, for example, the compound of Preparation Example (Ic-5) exhibited 100% relief after 14 days at a concentration of 0.004%.

Example E

Apple pie (Panonychus) test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: alkylaryl polyglycol ether 1 part by weight

1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier and the resulting concentrate is diluted with water to the desired concentration to prepare a suitable preparation of the active compound.

The plum trees (Prunus domestica) are soaked in the active compound preparation at the desired concentration and infected with the red spider (Panonychus ulmi) during the developing stage while the plants are damp.

After a certain period of time has elapsed, the percentage of relief is determined. 100% means that all spider mite has been killed, and 0% means that no spider mite has been killed.

In this test, for example, the compound of Preparation Example (Ic-4) exhibited a 100% relief ratio after 0.004% of the active compound concentration Messer 14 days.

Example F

Pre-germination test

Solvent: acetone 5 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

1 part by weight of the active compound is mixed with the abovementioned amount of the solvent, the above-mentioned amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration to prepare a suitable preparation of the active compound.

Seeds of test plants are seeded in standard soil, and after 24 hours the active compound preparation is irrigated. It is advantageous to keep the amount of water constant per unit area. The concentration of the active compound in the formulation is not critical and only the amount of active compound applied per unit area is an important factor. After 3 weeks, the degree of damage to the plant is graded as percent damage compared to the development of the untreated control.

The numbers indicate:

0% = no action (same as non-treated control)

100% = perfect test

In this test, the compounds of Production Examples (Ia-4), (Ib-6), (Ib-8), (Ic-4) and (Ic-5) One activity and crop selectivity.

Example G

Germination test

Solvent: acetone 5 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration to produce the appropriate preparation of the active compound.

The test plants having a height of 5 to 15 cm are sprayed with the active compound preparation so that a specific amount of the desired active compound per unit area is applied. After 3 weeks, the degree of damage to the plant is graded as percent damage compared to the development of the untreated control. The numbers indicate:

0% = no action (same as non-treated control)

100% = perfect test

In this test, for example, the compounds of Preparation Examples (Ia-4), (Ib-6), (Ib-8) and (Ic-4) clearly demonstrate superior activity and crop selectivity .

Example Ic-1 <

16.83 g (0.15 mol) of potassium tert-butylate were introduced into 100 ml of anhydrous DMF and 37.10 g (0.10 mol) of ethyl 2-O- (2,4-dichlorophenylacetyl) norbornane- 2-carboxylate is added dropwise at 0-10 [deg.] C, and the mixture is stirred at room temperature for 16 hours.

For the work-up, the reaction mixture is added dropwise to 500 ml of 1N hydrochloric acid, the precipitated product is filtered off and dried in a vacuum drying oven.

Yield: 29.79 g (92% of theory) White oil

Melting point: 227 DEG C

The compounds listed in Table 5 were prepared in a similar manner.

Table 5

Example Ib-1

3.25 g (10 mmol) of the compound (Ia-1) are introduced into 40 ml of anhydrous methylene chloride and 1.42 g (14 mmol) of triethylamine and one mole of DMAP are added, A solution of 0.94 g (12 mmol) of acetyl chloride in methylene chloride is added dropwise and the mixture is stirred at room temperature for 16 hours.

For work-up, the reaction mixture is washed with aqueous citric acid, NaHCO ₃ solution and NaCl solution, dried and evaporated in a rotary evaporator. And further purified by flash chromatography on silica gel using cyclohexane / ethyl acetate (3: 1).

Yield: 1.70 g (46% of theory) Solids

Melting point: 126 캜

The compounds shown in Table 6 were prepared in a similar manner.

Table 6

To a solution of 3.16 g (10 mmol) of compound (Ia-4) in 40 ml of anhydrous methylene chloride was added 1.42 g (14 mmol) of triethylamine and one drop of DMP, A solution of 1.38 g (13 mmol) of butyryl chloride in methylene chloride is added dropwise and the mixture is stirred at room temperature for 16 hours.

For work-up, the reaction mixture is washed with aqueous citric acid, NaHCO ₃ solution and NaCl solution, dried and evaporated in a rotary evaporator. The isomers are separated by flash chromatography on silica gel using cyclohexane / ethyl acetate (6: 1).

Nonpolar trans isomer

Yield: 0.92 g (24% of theory)

Melting point: 85-87 DEG C

And a polar cis isomer

Yield: 0.21 g (5% of theory)

Gradient: 125-126 C

Example Ic-1 <

3.25 g (10 mmol) of compound (Ia-1) are introduced into 40 ml of anhydrous methylene chloride and 1.42 g (14 mmol) of triethylamine and one mole of DMAP are added, A solution of 1.47 g (12 mmol) of isopropyl chloroformate in methylene chloride is added dropwise and the mixture is stirred at room temperature for 16 hours.

For work-up, the reaction mixture is washed with aqueous citric acid, NaHCO ₃ solution and NaCl solution, dried and evaporated in a rotary evaporator. And further purified by recrystallization from MTB ether / n-hexane.

Yield: 2.84 g (69% of theory) Solids

Melting point: 136 DEG C

The compounds shown in Table 7 were prepared in a similar manner.

Table 7

Example Id-1

One yen in anhydrous _{CH 2 C1 2 3.16g (10 mmol} ) in 40 ml of a (Ia-4), one Triethylamine of 1.52 g (15 mmol) in the following, from 0 to 10 ℃ 10 ml CH ₂ C1 ₂ was added dropwise a solution of SO ₂ Cl in the ₃ CM of 1.48g (13 mmol).

The mixture was stirred for 2 hours at room temperature, an aqueous citric acid solution in the following (10%), washed with NaHCO ₃ solution, dried and evaporated. The crude product is then mixed with 20 ml of petroleum ether, suction filtered and dried.

Yield: 2.40 g (61% of theory) Solids

Melting point: 130 to 155 DEG C

The compounds shown in Table 8 were prepared in a similar manner.

Table 8

Example Ie-1

To a solution of 2.2 g of Example No. Ia-4 in 10 ml of tetrahydrofuran is added 1.1 ml of triethylamine followed by 1.42 g (0.007 mol) of ethanethiophosphoric acid propyl thioether. The mixture is stirred at 50 < 0 > C for 3 hours, evaporated and the residue is chromatographed on silica gel using hexane / ethyl acetate / acetone (30/10/1) as eluent.

Yield: 2.1 g (62% of theory): viscous oil (isomer mixture)

^{1 H-NMR (300 MHz,} CDC1 3): δ = 2.19, 2.20, 2.25, 2.26 (4s, 9H, phenyl _{- CH 3), 3.15-3.25, 3.57} (2m, 1H, C H -OCH 3), 3.33 , 3.39 (2s, 3H, O CH 3), 6.87 (s, 2H, phenyl - H) ppm

^{31 P-NMR (162 MHz,} CDCl 3): δ = 119.05, 119.64 ppm.

The compounds shown in Table 9 were prepared in a similar manner.

Table 9

Example II-1

Example II-2

18.40 g (0.10 mol) of ethyl 2-hydroxy-norbornane-2-carboxylate and 24.59 g (0.11 mol) of 2,4-dichlorophenylacetyl chloride are refluxed in 100 ml of anhydrous toluene for 16 hours, Is evaporated in a rotary evaporator. The obtained compound was in the form of an oil in a yield of 37.10 g (quantitative).

The compounds shown in Table 10 were prepared in a similar manner.

Table 10

Claims (10)

The 3-aryl-4-hydroxy- - dihydrourilanone derivatives . In this formula, X represents alkyl, halogen, alkoxy or halogenoalkyl, Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl, Z represents alkyl, halogen or alkoxy, n represents a number of 0 to 3, Lt; RTI ID = 0.0 > X < / RTI > and Z, together with the phenyl radical to which they are attached, (Where Y is as defined above) to form a naphthalene radical, G is hydrogen (a) or group Lt; / RTI > A and B form an alkoxy, alkylthio, sulfonic poksil, alkylsulfonyl, carboxyl, or a cycle substituted by a C0 ^₂ R _2, together with the carbon atom to which they are attached, or A and B together with the carbon atoms to which they are attached form a cycle wherein two substituents together with the carbon atoms to which they are attached are optionally substituted by alkyl, alkoxy or halogen and which may be interrupted by oxygen or sulfur Represents a saturated cycle, Represents one equivalent of a metal ion or ammonium ion, L and M represent in each case oxygen or sulfur, R ¹ is an optionally substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, or cycloalkyl which may be interrupted by at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl , ≪ / RTI > hetaryl, phenoxyalkyl or hetaryloxyalkyl, R < ² > each represent optionally substituted alkyl, cycloalkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, or phenyl or benzyl, R ³ , R ⁴ and R ⁵ independently of one another are each independently alkyl optionally substituted by halogen, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, alkynylthio or cycloalkylthio, Substituted phenyl, phenoxy or phenylthio, R ⁶ and R ⁷ independently of one another denote hydrogen or represent alkyl, alkenyl, alkoxy or alkoxyalkyl, in each case optionally substituted by halogen, optionally substituted phenyl, or optionally substituted benzyl, or R ⁶ and R ⁷ together represent an alkylene radical optionally interrupted by oxygen or sulfur. A compound according to claim 1, wherein the group (G) has the meanings of (a), (b), (c), (d), (e), (f) and (g) 0.0 > (Ig) < / RTI > of formula (I) - dihydrofuranone derivatives. In this formula, A, B, E, L, M, X, Y, Z n, R 1, R 2, R 3, R 4, R 5, R 6 and R ⁷ are as defined in claim 1. The method according to claim 1, X is C _l-6 - represents a halogeno-alkyl, -alkyl, halogen, C _1-6 - alkoxy or C _1-3 Y represents hydrogen, C _1-6 -alkyl, halogen, C _1-6 -alkoxy or C 1- ₃ -halogenoalkyl, Z represents C _1-6 -alkyl, halogen or C _1-6 -alkoxy, n represents a number of 0 to 3, Lt; RTI ID = 0.0 > X < / RTI > and Z, together with the phenyl radical to which they are attached, (Wherein Y has the meaning as defined above) to form a naphthalene radical, A and B are C _l-6, together with the carbon atom to which they are attached -alkoxy, C _1-4 - alkylthio, C _l-4-sulfonic poksil alkyl, C _{1-4-alkylsulfonyl,} carboxyl, or CO ₂ R ² To form a saturated or unsaturated 3- to 8- A and B together with the carbon atoms to which they are attached form a C _{3-8 -cycle} wherein two substituents together with the carbon atoms to which they are attached represent C _1-6 -alkyl, C _1-6 -alkoxy or A saturated C _5-7 -ring optionally substituted by halogen and which may be interrupted by oxygen or sulfur, G is hydrogen (a) or group Lt; / RTI > here, Represents one equivalent of a metal ion or ammonium ion, L and M represent in each case oxygen or sulfur, R ¹ is an optionally halogen-substituted C _1-20 - alkyl, C _2-20 - alkenyl, C _l-8-alkoxy -C _1-8 - alkyl, C _{l-8-alkylthio-l} -C ₈ - alkyl, C _l-8 - _{poly-alkoxy-l} -C ₈ - alkyl, or halogen or a C _l-6 - C _3-8 which may be substituted by alkyl optionally being interrupted by at least one oxygen and / or sulfur atoms - cycloalkyl; Phenyl optionally substituted by halogen, nitro, C _1-6 -alkyl, C _1-6 -alkoxy, C _1-6 -halogenoalkyl or C _1-6 -halogenoalkoxy; Halogen, C _l-6 - alkyl, C _l-6 - alkoxy, C _l-6 - halogenoalkyl or C _l-6 - halogenoalkyl the alkoxy by optionally substituted phenyl -C _1-6 - alkyl; Hetaryl optionally substituted by halogen and / or Ci- ₆ -alkyl; Phenoxy-C _1-6 -alkyl optionally substituted by halogen and / or C _1-6 -alkyl; or Halogen, amino and / or C _1-6 - alkyl optionally substituted by a _{hat-aryloxy-l} -C ₆ - represents an alkyl, R ² is a C _l-20 optionally substituted by halogen, respectively -alkyl, C _3-20 - alkenyl, C _l-8-alkoxy -C _2-8 - alkyl, C _l-8-alkoxy poly _2- -C _8-alkyl, halogen or C _l-6-alkyl optionally substituted by a C _3-8 - cycloalkyl, or Each represent phenyl or benzyl optionally substituted by halogen, nitro, C _1-6 -alkyl, C _1-6 -alkoxy, C _1-6 -halogenoalkyl, R ^3, R ⁴ and R ⁵ are independently from each other by an optionally substituted C _l-8 - alkyl, C _l-8 - alkoxy, C _l-8 - alkylamino, di - (C _1-8 - alkyl) amino, C _1-8 -alkylthio, C _2-5 -alkenylthio, C _2-5 -alkynylthio or C _3-7 -cycloalkylthio, or represents a group selected from halogen, nitro, cyano, C _1-4 -alkoxy, C _{l-4-halogeno-alkoxy,} C _1-4 - alkylthio, C _{l-4-halogeno-alkylthio,} C _l-4 alkyl or C _l-4-a by halogenoalkyl, optionally substituted phenyl , Phenoxy or phenylthio, R ⁶ and R ⁷ are each independently represent hydrogen, respectively optionally substituted by halogen C _l-20 - alkyl, C _l-20 - alkoxy, C _3-8 - alkenyl or C _l-20-alkoxy- Ci _-2O -alkyl; Halogen, Ci _-20 -halogenoalkyl, Ci _-20 -alkyl or Ci _-20 -alkoxy; Or benzyl optionally substituted by halogen, C _{1- 20} -alkyl, C 1- ₂₀ -halogenoalkyl or C _1-20 -alkoxy, or R ⁶ and R ⁷ together are optionally blocked by oxygen or sulfur a C _4-6-3- of the formula (I) represents an alkyl renhwan aryl-4-hydroxy- - dihydrofuranone derivatives. The method according to claim 1, X is C _1-6 - alkyl, halogen, C _l-6 - alkoxy or C _1-2 - represents halogenoalkyl, Y represents hydrogen, C _1-6 -alkyl, halogen, C _1-6 -alkoxy or C _1-2 -halogenoalkyl, Z is C _{l-4-alkoxy-alkyl,} halogen or C _1-4 n represents a number of 0 to 2, Lt; RTI ID = 0.0 > X < / RTI > and Z, together with the phenyl radical to which they are attached, (Where Y is as defined above) to form a naphthalene radical, Alkyl sulfonyl, carboxyl, or C0 ^₂ R ₂ - A and B taken together with the bond to which they are tansowonga C _l-5 - alkoxy, C _1-3 - alkylthio, C _1-3 - alkyl sulfonic poksil, C _1-3 Form a saturated or unsaturated 5- to 7-membered ring, A and B together with the carbon atoms to which they are attached represent a C _{4-7 -triangle} wherein two substituents together with the carbon atoms to which they are attached represent C _{1 -3} -alkyl, C _{1 -3} -alkoxy, fluorine Or a saturated C _5-6 -ring optionally substituted by chlorine and which may be interrupted by oxygen or sulfur, G is hydrogen (a) or group Lt; / RTI > here, Represents one equivalent of a metal ion or ammonium ion, L and M represent in each case oxygen or sulfur, R ¹ is an optionally halogen in each case substituted by C _{l-16-alkyl, 1-16} C-alkenyl, C _l-6-alkoxy-l -C ₆ - alkyl, C _{l-6-alkylthio} -C _{l 6} - alkyl, C _l-6-alkoxy poly -C _l-6 - alkyl, or a chlorine or C _{l-4-optionally} substituted with alkyl optionally being interrupted by 1 to 2 oxygen and / or sulfur atoms C _3-7 -cycloalkyl; or Or phenyl optionally substituted by halogen, nitro, C _1-4 -alkyl, C _1-4 -alkoxy, C _1-3 -halogenoalkyl or C _1-3 -halogenoalkoxy, Halogen, C _l-4 - alkyl, C _l-4 - alkoxy, C _l-3 - halogenoalkyl or C _l-3 - by a halogeno alkoxy optionally substituted _phenyl-l -C ₄ -, or represents alkyl, Furanyl, thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl, each of which is optionally substituted by halogen and / or C _1-6 -alkyl; Phenoxy-Ci _-5 -alkyl optionally substituted by halogen and / or Ci _-4 -alkyl; or Each of halogen, amino and / or C _l-4 - a by alkyl optionally substituted pyridyloxy -C _1-5 - alkyl, _{pyrimidyl-oxy-l} -C ₅ - alkyl or thiazolyl _oxy-l -C ₅ - alkyl, Lt; / RTI > R ² is a halogen substituted in each case, C _l-6 - alkyl, C _3-6 - alkenyl, C _1-6 - alkoxy -C _2-6 - alkyl, C _l-6 - poly alkoxy -C _{2- 6} -alkyl, C _3-7 -cycloalkyl optionally substituted by fluorine, chlorine or C _1-4 -alkyl, or Each represent phenyl or benzyl, each of which is optionally substituted by halogen, nitro, C _1-4 -alkyl, C _1-3 -alkoxy or C _1-3 -halogenoalkyl, R ³ , R ⁴ and R ⁵ are each independently of the other C _1-6 -alkyl, C _1-6 -alkoxy, C _1-6 -alkylamino, di- (C _1-6 ) alkyl Amino, C _1-6 -alkylthio, C _3-4 -alkenylthio, C _2-4 -alkynylthio or C _3-6 -cycloalkylthio, or may be substituted by fluorine, chlorine, bromine, no, C _l-3 - alkoxy, C _l-3 - halogeno alkoxy, C _l-3 - alkylthio, C _l-3 - halogenoalkyl alkylthio, C _l-3 - alkyl or C _l-3 - halogenoalkyl Phenyl, phenoxy or phenylthio optionally substituted by alkyl, R ⁶ and R ⁷ are each independently represent hydrogen, respectively optionally substituted by halogen C _l-20 - alkyl, C _l-20 - alkoxy, C _3-8 - alkenyl or C _l-20-alkoxy- C _l-20 - represents an alkyl or halogen, C _l-5 - halogenoalkyl, C _l-5 - alkyl, C _l-5 - or represents a substituted phenyl optionally substituted by alkoxy, halogen, C _l-5 - alkyl, C _{l-5-halogeno-5-alkyl} or C _l - represents an alkoxy group optionally substituted by benzyl, or R ⁶ and R ⁷ is C _4-6, optionally blocked by an oxygen or sulfur together -alkyl 3-aryl-4-hydroxy-isoquinoline of general formula (I) - dihydrofuranone derivatives . The method according to claim 1, X represents methyl, ethyl, propyl, i-propyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl, Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl, Z represents methyl, ethyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy, n represents 0 or 1, A and B together with the carbon atom to which they are attached form a C _l-4 - alkoxy, C _l-2 - alkylthio, C _l-2 - alkyl sulfonic poksil, C _l-2 - alkylsulfonyl, carboxyl, or C0 ₂ R ² To form a saturated or unsaturated 5- to 6-membered ring, A and B together with the carbon atoms to which they are attached represent a C _{4-6 -cycle} wherein two substituents are taken together with the carbon atoms to which they are attached by methyl, ethyl, methoxy, ethoxy, fluorine or chlorine A saturated C _5-6 -ring optionally substituted and interrupted by oxygen or sulfur, G is hydrogen (a) or group Lt; / RTI > here, Represents one equivalent of a metal ion or ammonium ion, L and M represent in each case oxygen or sulfur, R ¹ is in each case optionally fluorine- or chlorine-substituted C _1-14 -alkyl, C _2-14 -alkenyl, C _1-4 -alkoxy-C _1-16 -alkyl, C _1-4 -alkylthio -C _l-6 - alkyl, C _l-4 - poly alkoxy -C _l-4 - alkyl, or fluorine, chlorine, optionally substituted by methyl or ethyl, 1 to 2 oxygen and / or be interrupted by a sulfur atom C < RTI ID = 0.0 > _3-6 -cycloalkyl < / RTI & Represents phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or nitro, C _1-3 -alkyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, Thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, When a phenoxy optionally substituted by fluorine, chlorine, methyl or _ethyl-l -C ₄ - alkyl or an exhibit, or by each of fluorine, chlorine, amino, methyl or ethyl optionally substituted _pyridyloxy-l -C ₄ - Alkyl, pyrimidyloxy-Ci _-4 -alkyl or thiazolyloxy-Ci _-4 -alkyl, R ² are each fluorine or chlorine, optionally substituted by a C _1-14 - alkyl, C _3-14 - alkenyl, C _1-4 - alkoxy -C _2-6 - alkyl, C _l-4 - poly alkoxy -C _2-6 -alkyl, C _3-6 -cycloalkyl optionally substituted by fluorine, chlorine, methyl or ethyl, or Each represent phenyl or benzyl optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl, R ^3, R ⁴ and R ⁵ are each other by each of the fluorine or chlorine independently optionally substituted C _l-4 - alkyl, C _l-4 - alkoxy, C _l-4 - alkylamino, di - (C _l-4 -alkyl) amino or C _l-4 - represent alkylthio or, respectively, fluorine, chlorine, bromine, nitro, cyano, C _l-2-alkoxy, C _{l-4-fluoro-alkoxy,} C _l-2-chloro alkoxy, C _l-2 - alkylthio, C _l-2 - fluoro-alkylthio, C _l-2 - chloro-alkylthio or C _l-3 - represents a phenyl, phenoxy or phenylthio optionally substituted by alkyl, optionally, R ⁶ and R ^7, independently of each other represents hydrogen or fluorine, respectively, by a chlorine or bromine, optionally substituted C _l-l0 - alkyl, C _3-6 - alkenyl, C _l-l0 - alkoxy or C _l-l0 -alkoxy -C _1-l0 - represents an alkyl or fluorine, chlorine, bromine, C _l-2 - halogenoalkyl, C _l-2-alkyl or C _l-4 - or represents a phenyl optionally substituted by alkoxy , fluorine, chlorine, bromine, C _l-4-a with an alkoxy represents an optionally substituted benzyl, or together are oxygen or by sulfur, optionally block - alkyl, C _{l-4-halogeno-C 1-4} alkyl, or 3-aryl-4-hydroxy-isoquinolines of general formula (I) representing a C _4-6 -alkylene ring, - dihydrofuranone derivatives . The compound of formula (II) In this formula, A, B, X, Y, Z and n have the meanings given in claim 1, R ⁸ is alkyl. a) acylating the 2-hydroxycarboxylic acid (ester) of the general formula (XIII) with a phenylacetyl halide of the general formula (XIV) and, if the hydroxycarboxylic acid of the general formula (IIa) Acyl-alpha-hydroxycarboxylic acid ester of general formula (II) according to claim 7. In this formula, A, B, X, Y, Z and n have the meanings given in claim 1, R ¹² represents hydrogen (compound of formula (XIIIa)) or alkyl (compound of formula (XIIIb)), Hal represents chlorine or bromine. The 3-aryl-4-hydroxy-isoquinolines of general formula (I) according to claim 1, - < / RTI > dihydrofuranone derivative. The 3-aryl-4-hydroxy-isoquinolines of general formula (I) according to claim 1, - < / RTI > dihydrofuranone derivative is mixed with an extender and / or a surfactant. The 3-aryl-4-hydroxy-isoquinolines of general formula (I) according to claim 1, Characterized in that the dihydrofuranone derivatives are applied to pests and / or their environment.