JPH1081675A - Herbicidal 1-substituted methyltetrazolinone compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a herbicide. SOLUTION: This new compound is shown by formula I (R<1> is a substitutable five-membered heterocycle bearing a heteroatom selected from N, S and O, oxiran-2-yl, chlorine-substitutable pyridyl or 1-4C alkyl-S(O)m; (m) is 0-2 or a 3-6C alicyclic hydrocarbon; R<2> and R<3> are each a 1-6C alkyl, 3-7C cycloalkyl, substitutable phenyl, or form a substitutable cycle together with an N atom; R<4> is H or methyl; (n) is 0 or 1), e.g. 1-(3-isoxazolylmethyl)-4-(N-isopropyl-N- phenylcarbamoyl)-5(4H)-tetrazolinone. The compound of formula I is obtained by reaction between compound of formula II and a compound of formula III (M is an eliminable group such as Cl or Br). This compound of formula I exhibits high herbicidal activity without showing no phytofoxicity to crops.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to novel 1-substituted methyltetrazolinones, a process for producing them and their use as herbicides. The present invention further relates to an intermediate for producing the 1-substituted methyltetrazolinones and a method for producing the intermediate.

[0002]

It is already known that certain tetrazolinones have herbicidal activity (EP-A-146,2).
79).

[0003] However, conventional tetrazolinones have not been sufficiently satisfactory in terms of herbicidal effect and chemical damage to crops.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted research to create a novel compound having high herbicidal activity and showing no phytotoxicity to crops. As a result, this time, a group of novel 1-
Substituted methyltetrazolinones were found.

[0005]

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Wherein R ¹ has ¹ to 3 heteroatoms arbitrarily selected from the group consisting of N, O and S, optionally substituted with halogen and / or C _1-4 alkyl. A good 5-membered heterocyclic group or oxiran-2-yl, chloro-substituted pyridyl,
C _1-4 alkyl-S (O) m-, wherein m represents 0, 1 or 2, or a C _3-6 alicyclic hydrocarbon group,
R ² and R ³ each independently represent C _1-6 alkyl, C _3-7 cycloalkyl or optionally substituted phenyl, or R ² and R ³ together with the N atom to which they are attached To form an optionally substituted ring, R ⁴ represents a hydrogen atom or methyl, and n represents 0 or 1.

The compound of the formula (I) of the present invention can be produced, for example, by the following production method a).

Production method a): Formula

[0009]

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Wherein R ¹ , R ⁴ and n are as defined above,

[0011]

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In the formula, R ² and R ³ have the same meanings as described above, and M is a compound represented by the formula (1), which represents a leaving group such as chloro or bromo.

The compounds of the formula (I) according to the invention have a strong herbicidal activity, in particular the EP-A-146,279.
The compounds of the invention exhibit a very good herbicidal effect and a good affinity for crops as compared to known compounds analogous to the compounds of the formula (I) described in Is extremely useful.

In the present invention, "5-membered heterocyclic group"
Includes a monovalent group consisting of a saturated, unsaturated or partially unsaturated 5-membered heterocyclic ring having the same or different 1 to 3 heteroatoms selected from the group consisting of N, O and S, Unsaturated, having 1 or 2 N atoms and 1 O or 1 S atom, or having 2 N atoms, or having 1 S or O atom A monovalent group consisting of a 5-membered heterocyclic ring, specifically, for example, isoxazolyl, pyrazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, thienyl, furyl, imidazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-thiadiazolyl and the like.

"Halogen" includes fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine.

The "C _3-6 alicyclic hydrocarbon group" is a saturated or partially unsaturated cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl and cyclopentyl. And cycloalkyl groups such as cyclohexyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl.

"Alkyl" can be straight or branched and includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl , N-hexyl and the like.

"Cycloalkyl" is a cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the substituent in the “optionally substituted phenyl” include, for example, halogen, C
_1-4 alkyl and the like, and the phenyl can be substituted with at least one, preferably 1-2 of these substituents.

In the "optionally substituted ring formed together with N atoms", the ring is a 5- to 6-membered monocyclic ring containing at least one, and preferably only one, N atom. Or a benzo-fused polycyclic heterocyclic ring represented by the formula (I)
In

[0021]

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Examples of the cyclic group which can be formed by 1,2,3-dihydroquinolin-1-yl, 1,2,3,4-tetrahydroquinolin-1-yl and the like are included. These rings may be optionally substituted, and examples of the possible substituents include C _1-4 such as methyl and ethyl.
Halogen such as alkyl, fluoro, chloro and the like,
Preferably it is methyl or fluoro.

A preferred group of compounds of the present invention include those of formula (I) wherein R ¹ is one or two N atoms and one O atom.
A 5-membered hetero atom having one atom or one S atom, two N atoms, or one N or O atom, optionally substituted by chloro and / or methyl A cyclic group, or oxiran-2-yl, optionally substituted chloro-substituted pyridyl, C _1-3 -alkylthio, methylsulfinyl, methylsulfonyl, cyclopropyl, cyclopentenyl or cyclohexyl, R ² and R ³ independently represents C _1-4 alkyl, C _5-6 cycloalkyl, optionally substituted phenyl wherein the substituent is halogen or C _1-4 alkyl, or R ² And R ³ are the N
Together with the atom, optionally substituted 1,2-dihydroquinolin-1-yl or 1,2,3,4-tetrahydroquinolin-1-yl, wherein the substituent is methyl or fluoro A) and R ⁴ represents a hydrogen atom and n represents 0 or 1.

In a more preferred group of compounds, in the above formula (I), R ¹ is isoxazolyl, pyrazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, thienyl or furyl. And these groups may be substituted with chloro and / or methyl, or oxiran-2-yl, 3-pyridyl, 6-chloro-3-pyridyl, methylthio, n-propylthio, isopropylthio, methylsulfinyl , Methylsulfonyl, cyclopropyl, cyclopentenyl or cyclohexyl, wherein R ² and R ³ are each independently C _1-3 alkyl, cyclohexyl or optionally substituted phenyl (where the substituent is fluoro, chloro, or shows a bromine or methyl), or R ² and R ³ be bonded thereof Together with the N atom, 6-fluoro-2,2-dimethyl-1,2,3,4-tetrahydroquinolin-1-yl, 2-methyl-1,2,3,4-tetrahydroquinolin-1- Yl, 2,2-dimethyl-1,2-dihydroquinolin-1-yl, 6-fluoro-2,2-dimethyl
-1,2-dihydroquinolin-1-yl or 2,2-dimethyl-
1,2,3,4-Tetrahydroquinolin-1-yl may be formed, including compounds wherein R ⁴ represents a hydrogen atom and n represents 0 or 1.

The process a) for the preparation of the compounds of the formula (I) described above uses, for example, 1- (3-isoxazolylmethyl)
The reaction formula for using -5 (4H) -tetrazolinone and N-isopropyl-N-phenylcarbamoyl chloride is as follows.

[0026]

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In the above process a), the starting compound of the formula (II) is a novel compound, for example, the following process b)
To f).

Production method b) : Formula

[0029]

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Wherein R ¹ , R ⁴ and n have the same meanings as defined above, and trimethylsilyl azide;
Reacting in the presence of a catalytic amount of boron trifluoride etherate or in process c) : reacting the compound of formula (IV) with sodium azide in a polar solvent in the presence of a catalytic amount of ammonium chloride Or the manufacturing method d) : Formula

[0031]

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Wherein R ¹ , R ⁴ and n have the same meanings as defined above, and are reacted with trimethylsilyl azide, or the production method e) :

[0033]

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Wherein R ¹ , R ⁴ and n are as defined above,

[0035]

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In the formula, M represents a hydrogen atom or methyl, or it is reacted with a compound represented by the formula: or f) : when R ¹ represents a group other than C _1-4 alkyl-S (O) m- ,formula

[0037]

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Wherein R ¹¹ represents a group defined for R ¹ other than C _1-4 alkyl-S (O) m-, and R ⁴ and n
Is reacted with sodium periodate in the presence of a catalytic amount of osmium oxide [VIII].

In the formula (I), R ¹ is an alkyl
In the case where (C _1-4 ) sulfinyl and alkyl (C _1-4 ) sulfonyl represent a compound, R ¹ is an alkyl (C
_1-4 ) The compound corresponding to thio is oxidized according to a general oxidation method, whereby the corresponding alkyl (C _1-4 ) sulfinyl form or the corresponding alkyl (C _1-4 ) sulfonyl form can be easily obtained. it can.

Further, in the formula (I), when R ¹ represents oxiran-2-yl, the compound may be, alternatively, 1- (2-propenyl) as exemplified in Synthesis Example 5 below. It can also be obtained by oxidizing (4-N, N-disubstituted carbamoyl) -5 (4H) -tetrazolinone with m-chloroperoxybenzoic acid.

In the formula (I), when R ¹ represents 3-methyl-2-isoxazolin-5-yl, the compound is preferably prepared as another method, as exemplified in Synthesis Example 6 below. It can be obtained according to a method known per se described in Houben-Weyl, 1985, E5, pp. 1591-1610. The starting tetrazolinones used in Synthesis Example 6 are known compounds described in Japanese Patent Application Laid-Open No. 8-259,947.

The compound of the formula (IV) used as a raw material in the above-mentioned processes b) and c) includes isocyanates known in the field of organic chemistry. 14, 1490 to 1503 (published by Maruzen on December 20, 1977).

The compound of the formula (V) used as a raw material in the above-mentioned production method d) also includes acid chlorides known in the field of organic chemistry. Volume, pages 1104 to 1120 (published by Maruzen on December 20, 1977). For example, the expression

[0044]

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In the formula, R ¹ , R ⁴ and n have the same meanings as defined above, and can be easily obtained by reacting a carboxylic acid represented by the formula with thionyl chloride as a halogenating agent.

The compounds of the above formula (IX) are described, for example, in "New Experimental Chemistry Course", edited by The Chemical Society of Japan, Vol.
It can be synthesized using the method described on page 1000 (issued by Maruzen on December 20, 1977), or can be easily obtained by hydrolyzing the corresponding carboxylic acid ester.

The compound of the formula (VI) used as a raw material in the above process e) is described, for example, in Berichte, vol. 2
8, pp. 74-76 (1895)

[0048]

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In the formula, R ¹ , R ⁴ and n have the same meanings as described above, and can be produced by reacting a compound represented by the following formula with sodium azide.

The dithiocarbamic acid ester of the above formula (XI) is, for example, a compound of the formula

[0051]

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In the formula, R ¹ , R ⁴ and n have the same meanings as defined above, or are reacted with a compound represented by the formula

[0053]

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Wherein R ¹ , R ⁴ and n have the same meanings as defined above, and the compound is reacted with carbon disulfide.
Further, it can be easily obtained by reacting with a methylating agent such as dimethyl sulfate or iodomethane.

The compounds of the above formula (XII) are described, for example, in “New Experimental Chemistry Course”, edited by The Chemical Society of Japan, vol. 14, 1503-150.
It can be produced according to the method described on page 9 (issued by Maruzen on December 20, 1977).

Further, the compound of the above formula (XIII) is described in "New Experimental Chemistry Course", edited by The Chemical Society of Japan, Vol. 14, 1332-1399.
The compound can be synthesized by the method described on page (December 20, 1977, published by Maruzen).

The compounds of the formula (VII) used as raw materials in the above-mentioned process e) are known per se,
Specific examples include ethylene oxide and 1,2-epoxypropane.

The compound of the formula (VIII) used as a raw material in the above-mentioned production method f) is, for example, 1-ethenyl-5 (4
H) -tetrazoline of the formula

[0059]

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In the formula, R ¹ , R ⁴ and n have the same meanings as described above, and Hal represents a halogen.

The 1-ethenyl- used in the above reaction
5 (4H) -tetrazolinone is a known compound, and the compound of formula (XIX) is also a well-known compound in the field of organic chemistry.

Typical examples of the compound of the formula (II) are as follows.

1- (1-cyclopentenylmethyl) -5
(4H) -tetrazolinone, 1- (2-tetrahydrofurfuryl) -5 (4H) -tetrazolinone, 1- (5-methyl
-3-isoxazolylmethyl) -5 (4H) -tetrazolinone, 1- (3-isoxazolylmethyl) -5 (4H)-
Tetrazolinone, 1- (3,5-dimethyl-4-isoxazolylmethyl) -5 (4H) -tetrazolinone, 1- (5-
Chloro-1,3-dimethyl-4-pyrazolylmethyl) -5 (4
H) -tetrazolinone, 1- (5-isoxazolylmethyl) -5 (4H) -tetrazolinone, 1- (4-methyl-1,
2,5-oxadiazol-3-ylmethyl) -5 (4H)-
Tetrazolinone, 1- (4-chloro-5-isoxazolylmethyl) -5 (4H) -tetrazolinone, 1- (5-methyl
-1,3,4-oxadiazol-2-ylmethyl) -5 (4
H) -Tetrazolinone, 1- [2- (3-methylisoxazol-5-yl) ethyl] -5 (4H) -tetrazolinone, 1- [1- (3-methylisoxazol-5-ylmethyl) ethyl]- 5 (4H) -tetrazolinone, 1- (cyclohexylmethyl) -5 (4H) -tetrazolinone,
-(Cyclopropylmethyl) -5 (4H) -tetrazolinone, 1- (6-chloro-3-pyridylmethyl) -5 (4H)-
Tetrazolinone, 1- (4-thiazolylmethyl) -5 (4
H) -tetrazolinone, 1- (4-isothiazolylmethyl) -5 (4H) -tetrazolinone, 1-methylthiomethyl-5 (4H) -tetrazolinone, 1-n-propylthiomethyl-5 (4H) -tetrazolinone, etc. .

On the other hand, the compound of the formula (III) reacted with the compound of the above formula (II) is a carbamoyl chloride well-known in the field of organic chemistry, and typical examples thereof are as follows. .

N, N-diethylcarbamoyl chloride,
N-cyclohexyl-N-ethylcarbamoyl chloride, N, N-di-isopropylcarbamoyl chloride,
N-ethyl-N-isopropylcarbamoyl chloride,
N-methyl-N-isopropylcarbamoyl chloride,
N-isopropyl-N-phenylcarbamoyl chloride, N-4-fluorophenyl-N-isopropylcarbamoyl chloride, N-4-chlorophenyl-N-isopropylcarbamoyl chloride, N-isopropyl-N-p-tolylcarbamoyl chloride, N -4-Bromophenyl-
N-isopropylcarbamoyl chloride, 2,2-dimethyl-1,2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 2-methyl-1,2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, N-ethyl-
N-phenylcarbamoyl chloride, Nn-propyl-
N-phenylcarbamoyl chloride, N-cyclohexyl-N-isopropylcarbamoyl chloride, 2,2-dimethyl-1,2-dihydroquinolin-1-ylcarbonyl chloride, 6-fluoro-2,2-dimethyl-1,2- Dihydroquinolin-1-ylcarbonyl chloride, 6-fluoro-2,2-dimethyl-1,2,3,4-tetrahydroquinoline
-1-ylcarbonyl chloride and the like.

The reaction of the production method a) is usually carried out in an organic solvent inert to the reaction. Examples of inert organic solvents that can be used in the reaction include aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane,
Petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, tetrachlorocarbon,
1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); nitrile , For example, acetonitrile, propionitrile; acid amides, for example,
Dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-
Examples thereof include 2-imidazolidinone and hexamethylphosphotriamide (HMPA).

Process a) can be carried out in the presence of a base, and a preferred example of a base that can be used is 4-dimethylaminopyridine (DMAP).

When DMAP is used as the base, the reaction of the production method a) can be carried out usually at a temperature in the range of about -10 to about 200 ° C, preferably about 25 to about 140 ° C under normal pressure. In some cases, the reaction can be carried out under pressurized or reduced pressure conditions.

The reaction of the production method a) can be carried out using a base other than DMAP. Examples of such a base include inorganic salts (for example, sodium carbonate, potassium carbonate, sodium hydroxide, and hydroxide). Potassium alcohols), alkyl alcoholates (eg, sodium methoxide,
Sodium ethoxide, calcium-tert-butoxide, etc.), sodium hydroxide, potassium hydroxide, lithium hydroxide, organic bases (eg, triethylamine, 1,1,
4,4-tetramethylethylenediamine, N, N-dimethylaniline, pyridine and the like).

When the reaction is carried out using these bases, the compound of the formula (I) can be selectively obtained by using DMAP as a catalyst.

The reaction temperature in this case is usually from about 0 to about 1
The reaction can be carried out at 50 ° C., preferably in the range of about 25 ° C. to about 100 ° C., and the reaction is desirably carried out under normal pressure. is there.

Thus, the compounds of formula (I) of the present invention
For example, about 1 mol to about 1.5 mol of the compound of the formula (III) is added to DMAP as a base for 1 mol of the compound of the formula (II).
It can be produced by reacting in an inert solvent as described above in the presence of about 1 mol to about 1.5 mol.
Further, as another example, the compound of the formula (I) is obtained by adding about 1 mol to about 1.5 mol of the compound of the formula (III) to about 0.01 mol of DMAP as a catalyst per 1 mol of the compound of the formula (II). It can also be prepared by reacting in an inert solvent as described above in the presence of from about 1 mol to about 0.3 mol and about 1 mol to about 1.5 mol of potassium carbonate as a base, for example.

The thus-obtained compound of the formula (I) of the present invention can be isolated and purified by, for example, crystallization, chromatography and the like.

On the other hand, the reaction of the above-mentioned production method b) can be carried out using a boron trifluoride etherate complex as a catalyst. The reaction temperature is usually about 0 to about 200 ° C., preferably about 50 to about 150 ° C., and the reaction is desirably carried out under normal pressure. It is also possible to do.

In the process b), about 1 mol to about 2 mol of trimethylsilyl azide is usually added to 1 mol of the compound of the formula (IV), and about 0.0 mol of boron trifluoride etherate complex as a catalyst is used.
The reaction can be carried out in the presence of from 0.05 mol to about 0.01 mol.

The reaction of the production method c) is usually carried out in a polar solvent. Examples of the polar solvent that can be used include acid amides such as dimethylformamide and dimethylacetamide; and sulfoxides such as dimethylsulfoxide and sulfolane. be able to. The reaction temperature is generally about 0 to about 200 ° C., preferably about 20 to about 150 ° C., and the reaction is desirably carried out under normal pressure. It is also possible to do.

The process c) is usually carried out by adding about 1 mol to about 1.5 mol of sodium azide to about 0.05 mol to about 1 mol of aluminum chloride as a catalyst per 1 mol of the compound of the formula (IV). It can be carried out by reacting in the presence of a polar solvent such as dimethylformamide.

The reaction of the above-mentioned process d) can be carried out, for example, at a temperature of about 0 to about 200 ° C., preferably about 25 to about 130 ° C. under normal pressure. It is also possible to do.

Process d) can be usually carried out by reacting about 2 mol to about 4 mol of trimethylsilyl azide with respect to 1 mol of the compound of the formula (V).

The reaction of the above-mentioned production method e) is usually carried out in a solvent inert to the reaction. Examples of the inert solvent usable in this case include water, alcohols (eg, methanol, ethanol, isopropanol, etc.). Can be mentioned.

The reaction of the production method e) can be carried out in the presence of a base, for example, an inorganic base (for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc.). it can.

The reaction temperature in the process e) is usually about-
The reaction can be carried out at a temperature of 30 to about 50 ° C., preferably about 0 to about 30 ° C., and the reaction is desirably carried out under normal pressure, but may be carried out under pressure or reduced pressure in some cases. .

In the production method e), usually, about 1 mol to about 1.3 mol of the compound of the formula (VII) is reacted with 1 mol of the compound of the formula (VI) in an inert solvent in the presence of a base. Can be carried out.

The reaction of the above-mentioned production method f) can be usually carried out in a solvent inert to the reaction, for example, water,
Alcohols (eg, ethanol), ethers (eg, dioxane), carbon tetrachloride, and the like can be given.

The reaction temperature of the production method f) is usually about -30 to
The temperature can be about 50 ° C., preferably about 0 to about 40 ° C., and the reaction is desirably carried out under normal pressure.
Depending on the case, it is also possible to carry out under a pressurized or reduced pressure condition.

The process f) is usually carried out with the compound 1 of the formula (VIII)
The reaction can be carried out by reacting about 2 to about 3 moles of sodium periodate in an inert solvent in the presence of a catalytic amount of osmium oxide [VIII].

The active compound of the formula (I) of the present invention has an excellent herbicidal activity as shown in the test examples described below.
It can be used as a pesticide, especially as a herbicide for controlling weeds. Here, "weeds" broadly means all plants that grow in undesirable places.

The compounds of the present invention act as non-selective or selective herbicides depending on the concentration used. The active compounds according to the invention can be used, for example, as selective herbicides between the following weeds and cultivated plants.

Dicotyledon weeds: mustard (Sinapis), mamegunbaizuna (Leipidium), Yaegura kinutaso (Ga)
lium), Chickweed (Stellaria), Akaza Aritasou (Che)
nopadium), nettle (Urtica), hangengsou noborogiku kion (Senecio), Amaranth
us), Purslane Matsubaboton (Portulaca), Onamimomi (Xanthium), Morning Glory (Ipomoea), Honey Willow (Pol
ygonum), ragweed (Ambrosia), and thistle and foxtail
(Cirsium), Nogeshi (Sonchus), Eggplant potato (So
lanum), brown pepper (Rorippa), and odoris (Lamiu
m), stag beetle, Veronica, Datura, Datura, Sumirepanji (Viola), Chishimadoro (Galeopsis), poppy (Papaver), cornflower (Centaure), swordfish (Galinsoga), kikaalagusa (R) Lindernia) et al.

Dicot cultivated plants: cotton (Gossypium), soybean (Glycine), Fudansou satodancon (Beta),
Carrot (Daucus), kidney bean / Aiomada (Phase
olus), peas (Pisum), eggplant potatoes (Solanu)
m), Flax (Linum), Sweet Potato Asagao (Ipomoea),
Broad bean Nantenhagi (Vicia), tobacco (Nicotian)
a), tomato (Lycopersicon), peanut (Arachi
s), Brassica cabbage cabbage cabbage (Brassic
a), Lactuca, cucumber melon (Cucu
mis), pumpkin (Cucurbita), etc.

Monocotyledon weeds: Echinochloa, Echinokoro millet (Setaria), millet (Panicum), mexican (Digi)
taria), Awaegari timothy (Phleum), Strawberry squirrel, Poa annua (Poa), Boletta terrestris (Festuca), Ohishiba shikokue (Eleusine), Lokium (Lolium), Kitsuneya oat (Bromus oat), Bromus oat (Bromus oat) (Avena), Cyperus papyrus schisuiwei (Cyperus), Sorghum, Sorghum (Agropyron), Konagi (Mo)
nocharia), Tentsuki (Fimbristylis), Omodaka Kwai (Sagittaria), Harii Krogwai (Eleocharis),
Fireflies, Ukiagura-futoi (Scirpus), Sparrow Butterfly (Paspalum), Platypus (Ischaemum), Nukabo (Agr)
ostis), Alopecurus, Cynodon and the like.

Monocotyledon cultivation plants: rice (Oryza), corn hopcorn (Zea), wheat (Triticum), barley (Hordeum), oats oats (oat)
(Avena), rye (Secale), sorghum (Sorghum),
Millet (Panicum), Sugarcane Vaseobana (Saccharu)
m), pineapple (Ananas), asparagus (Asparagu)
s), green onion leek (Allium) and so on.

The use of the active compounds of the formula (I) according to the invention is
The present invention is not limited to the above plants, and can be similarly applied to other plants. Further, depending on the concentration used, the active compound of the present invention can control weeds non-selectively.For example, it can be used in industrial land such as factories, railway tracks, roads, tree plantations, and non-tree plantations. it can.

In addition, the active compounds according to the invention can be used for weed control in perennial plant cultivation, for example plantations, ornamental plantations, orchards, vineyards, citrus orchards, nut orchards, Banana plantation, coffee plantation, tea plantation, rubber plantation, guinea oil palm plantation,
The present invention can be applied to cocoa cultivation sites, small orchards, hop cultivation sites, and the like, and can be applied to selective weed control in annual plant cultivation.

The active compounds of the formula (I) according to the invention can be brought into the customary pharmaceutical forms for use. Such formulations include, for example, solutions, emulsions, wettable powders,
Suspensions, powders, soluble powders, granules, tablets, suspension emulsion concentrates, microcapsules in polymeric substances, jumbo preparations and the like can be mentioned.

These preparations can be prepared in a manner known per se, for example, by adding the active compound to a spreading agent, ie, a liquid and / or solid diluent, if necessary with a surfactant. Ie emulsifier and / or dispersant and / or
Alternatively, it can be produced by mixing with a foam forming agent or the like.

Examples of the liquid diluent include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride, Methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc. or paraffins (eg, mineral oil fraction, mineral and vegetable oils, etc.)], alcohols (eg, butanol, glycol and ethers and esters thereof), ketones (Eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.), water and the like. When water is used as the spreading agent, an organic solvent can be used as an auxiliary solvent.

Examples of the solid diluent include ammonium salts, soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite, diatomaceous earth, etc.) and soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silica, etc.). Acid salts and the like). Solid carriers for granules include, for example, crushed and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, fine particles of organic substances ( For example, sawdust, coconut, corn cob, tobacco stem, etc.).

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers (eg, alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates, etc.]] and albumin hydrolysis products.

Suitable dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Fixing agents can also be used, if necessary, in the preparations (powder, granules, jumbo, emulsion). Examples of such fixing agents include carboxymethylcellulose, natural and synthetic polymers (eg, Arabic). Rubber, polyvinyl alcohol, polyvinyl acetates, etc.), natural phospholipids (eg, cephalins and lecithins),
Examples include synthetic phospholipids. Further, mineral oils and vegetable oils can be used as additives.

Colorants may be added. Examples of the colorants include inorganic pigments such as iron oxide, titanium oxide and Prussian blue; organic dyes such as alizarin dye, azo dye and metal phthalocyanine dye; Iron, manganese,
Trace elements such as salts of metals such as boron, copper, cobalt, molybdenum, zinc and the like can be mentioned.

The preparations generally contain the active ingredient in an amount of 0.1%.
It can be contained in the range of 1 to 95% by weight, preferably 0.5 to 90% by weight.

The active compounds according to the invention can be used as such or in the form of their formulations for controlling weeds and can also be used as mixtures with known herbicides. May be prepared in a final preparation form in advance, or may be mixed in a tank at the time of use.

The active compounds of the formula (I) according to the present invention
Mixtures with safeners are also possible, which allows for a wider application as a selective herbicide.

As the safener, 1- (α, α-dimethylbenzyl) -3-p-tolylurea can be exemplified.

The active compounds of the formula (I) according to the invention can be used as such or in the form of preparations according to the customary methods, for example
Watering, spraying
g, atomizing), dusting or granulation.

The active compounds of the formula (I) according to the invention can be applied both before and after germination of the plants. They can also be incorporated into the soil before sowing.

The application rate of the active compound is not strictly limited, and the desired effect, the type of the target plant,
It can be varied over a wide range depending on the place of application, the time of application, etc., but as a rough guide, about 0.001 kg to about 10 k as active compound per hectare
g, preferably in the range of about 0.01 kg to about 5 kg.

Next, the production and use of the compound of the present invention will be described more specifically with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In addition,
“Parts” are “parts by weight” unless otherwise specified.

[0111]

【Example】

 Synthesis Example 1

[0112]

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1- (3-isoxazolylmethyl) -5-
(4H) -tetrazolinone (0.6 g), 4-dimethylaminopyridine (0.5 g) and N-isopropyl-N-phenylcarbamoyl chloride (0.8 g) are suspended in toluene (30 ml), and then suspended at 50 to 55 ° C. And stir for 5 hours. After cooling, the organic layer was washed with water, 1N hydrochloric acid, water, and saturated saline in this order. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (ethanol / chloroform = 2/100) to give 1- (3-isoxazolylmethyl) -4-. (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (1.0 g) was obtained. mp. 110-11
2 ℃ Synthesis Example 2

[0114]

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1- (4-Chloro-1,3-dimethyl-5-pyrazolylmethyl) -5- (4H) -tetrazolinone (0.4
g) 4-dimethylaminopyridine (0.26 g) and N
-Isopropyl-N-phenylcarbamoyl chloride (0.41 g) was suspended in toluene (50 ml).
Stir at ~ 55 ° C for 5 hours. After cooling, the organic layer was washed with water, 1N hydrochloric acid, water, and saturated saline in this order. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (ethanol / chloroform = 2/150) to give 1- (4-chloro-1,3-dimethyl-5). -Pyrazolylmethyl) -4- (N-isopropyl-N
-Phenylcarbamoyl) -5 (4H) -tetrazolinone (0.6 g) was obtained. mp. 158.5-159.5 ° C Synthesis Example 3

[0116]

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1-Cyclohexylmethyl-5- (4H) -tetrazolinone (0.6 g), 4-dimethylaminopyridine (0.45 g) and N-isopropyl-N-phenylcarbamoyl chloride (0.72 g) were added to toluene. Suspend and stir at 50-55 ° C for 5 hours. After cooling, the organic layer was washed with water, 1N hydrochloric acid and saturated saline in this order. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (chloroform 100).
%) To give 1-cyclohexylmethyl-4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.9 g). mp. 79-81.5 ° C Synthesis Example 4

[0118]

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1-Cyclopropylmethyl-5- (4H) -tetrazolinone (0.7 g), 4-dimethylaminopyridine (0.8 g) and N-isopropyl-N-phenylcarbamoyl chloride (0.8 g) were dissolved in toluene. Suspended in 5
Stirred at 0-55 ° C for 6 hours. After cooling, the organic layer was washed with water, dilute hydrochloric acid and then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (chloroform) to give 1-cyclopropylmethyl-4- (N-isopropyl-
N-phenylcarbamoyl) -5 (4H) -tetrazolinone (1.4 g) was obtained. mp. 67 to 69 ° C Compounds obtained by the same method as in Synthesis Examples 1 to 4 are shown in Table 1 together with the compounds obtained in Synthesis Examples 1 to 4.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

[Table 10]

[0130]

[Table 11]

[0131]

[Table 12]

Synthesis Example 5

[0133]

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1- (2-propenyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.8 g) and m-chloroperoxybenzoic acid (1.5 g) It was dissolved in methylene chloride (50 ml) and stirred at room temperature for 6 hours. After the reaction mixture was washed with water, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (chloroform).
To give 1- (2,3-epoxypropyl) -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.5 g). n ²⁰ _D 1.5289 Synthesis Example 6

[0135]

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To a toluene solution (20 ml) of 1- (3-butenyl) -4- (N-isopropyl-N-phenylcarbamoyl) 5 (4H) -tetrazolinone (1.0 g) and phenylisocyanate (0.9 g) At room temperature, a toluene solution (10 ml) of nitroethane (0.4 g) and triethylamine (0.9 g) was added dropwise.
Further, the reaction was allowed to proceed at room temperature for 18 hours, and the precipitate was removed by filtration. The toluene solution was washed with water, diluted hydrochloric acid, and further with water, and dried over anhydrous magnesium sulfate. After the toluene was distilled off, the obtained residue was purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 1: 1) to give the desired 1-hexane.
[2- (3-Methyl-2-isoxazolin-5-yl) ethyl] -4- (N-isopropyl-N-phenylcarbamoyl) -5 (4H) -tetrazolinone (0.7
g) was obtained as crystals. mp. 76.5-79.5 ° C Synthesis Example 7

[0137]

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A mixture of 3-isoxazolylmethyl isocyanate (3.9 g), trimethylsilyl azide (7.5 g) and a catalytic amount of boron trifluoride etherate was mixed with 40
Heated to reflux for an hour. After cooling, excess trimethylsilyl acid was distilled off under reduced pressure, and methanol was added to the residue. Thereafter, methanol was distilled off under reduced pressure, and the residue was subjected to column chromatography (ethanol / chloroform 10/10).
0) and 1- (3-isoxazolylmethyl) -5-
(4H) -tetrazolinone (4.5 g) was obtained. mp. 7
6-79 ° C Synthesis Example 8

[0139]

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4-Chloro-5-chloromethyl-1,3-dimethylpyrazole (5.0 g), 4-dimethylaminopyridine (3.0 g) and 1-ethenyl-5- (4H) -tetrazolinone (2.5 g) ) Is suspended in acetonitrile (100 ml) and stirred at 50-55 ° C. for 5 hours. After cooling, the solvent is distilled off under reduced pressure, water (100 ml) is added, and the mixture is extracted with methylene chloride. And the organic layer is water, 1N hydrochloric acid,
Washing was performed in the order of water and saturated saline. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (ethanol / chloroform = 2 /
100) and purified by 1- (4-chloro-1,3-dimethyl-5).
-Pyrazolylmethyl) -4-ethenyl-5 (4H) -tetrazolinone (4.2 g) was obtained. mp. 78-79.5 ° C Synthesis Example 9

[0141]

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1- (4-Chloro-1,3-dimethyl-5-pyrazolylmethyl) -4-ethenyl-5 (4H) -tetrazolinone (0.6 g) was treated with dioxane (30 ml) and water (10 ml).
ml), a catalytic amount of osmium (VIII) is added, and the mixture is vigorously stirred for 30 minutes. Further, sodium periodate (1.5 g) is added and the mixture is stirred for 12 hours. The reaction mixture is filtered, the solvent is distilled off under reduced pressure until the volume becomes 1/4, water (50 ml) is added, and the mixture is extracted with methylene chloride. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 1- (4-chloro-1,3-5-dimethyl) pyrazolylmethyl) -5 (4H) -tetrazolinone (0.4 g). . mp. 157 to 158.5 ° C Synthesis Example 10

[0143]

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Cyclohexylmethyl isocyanate (6.0 g), trimethylsilyl azide (10 g) and a catalytic amount of boron trifluoride etherate were mixed and heated under reflux for 50 hours. After cooling, excess trimethylsilyl azide was distilled off under reduced pressure, and methanol was added to the residue. Thereafter, methanol was distilled off under reduced pressure, the residue was purified by column chromatography (chloroform = 100%), and 1-cyclohexylmethyl-5 (4H) -tetrazolinone (9.
8 g) were obtained. mp. 88-89 ° C Synthesis Example 11

[0145]

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Cyclopropylmethylamine (14.2)
g) and potassium tert-butoxide (22.5 g) in methanol were added dropwise with carbon disulfide (20 g) under ice-cooling. 30 minutes later, under the same conditions, dimethyl sulfate (25.2 g)
Was added and reacted for 1 hour. Water was added to the reaction solution, extracted with toluene, and the toluene layer was washed with water. After the toluene solution was dried over anhydrous magnesium sulfate, the toluene was distilled off and methylcyclopropylmethyldithiocarbamate (26.
3 g) was obtained. An aqueous solution of sodium azide (12.7 g) was added to the obtained dithiocarbamate, and the mixture was reacted at 100 ° C. until the generation of methyl mercaptan was completed. After cooling, the reaction solution was washed with ethyl acetate. Ethyl acetate was added to the aqueous layer, acidified with diluted hydrochloric acid, and the acidic substance was extracted with ethyl acetate. The ethyl acetate solution was washed with saturated saline, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to give 1-cyclopropyltetrazoline-5-thione (10%).
g) was obtained. This grade was treated with sodium hydroxide (3.2
g) was dissolved in an aqueous solution (10 ml), and propylene oxide (6 g) was added under ice cooling. The reaction was stirred overnight.
The reaction solution was acidified with concentrated hydrochloric acid, extracted with chloroform,
The organic layer was washed with brine and dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (n-hexane-ethyl acetate 1: 1) to obtain 1-cyclopropylmethyl-5- (4H) -tetrazolinone (5.0 g). mp. 61-64 ° C Synthesis Example 12

[0147]

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Cyclopentylideneacetic acid chloride (5.
A mixture of 6 g) and trimethylsilyl azide (9.8 g) was heated to reflux at 100 to 130 ° C. for 48 hours. After cooling, unreacted trimethylsilyl azide was distilled off under reduced pressure, and methanol was added to the residue. The methanol was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (n-hexane-ethyl acetate 2: 1 to 1: 1).
(1-cyclopentenylmethyl) -5 (4H) -tetrazolinone (0.7 g) was obtained. The main product is 1-cyclopentylidenemethyl-5 (4H) -tetrazolinone (3.2 g)
Met. mp. 91 to 93 ° C Compounds obtained in the same manner as in Synthesis Examples 7 and 9 to 12 are shown in Table 2 together with the compounds obtained in Synthesis Examples 7 and 9 to 12 described above.

[0149]

[Table 13]

[0150]

[Table 14]

[0151]

[Table 15]

The compounds obtained in the same manner as in Synthesis Example 8 are shown in Table 3 together with the compounds obtained in Synthesis Example 8.

[0153]

[Table 16]

Test Example 1 : Soil treatment test before germination for upland weeds Preparation method: carrier: acetone 5 parts by weight Emulsifier: benzyloxy polyglycol ether 1 part by weight 1 part by weight of the active compound was added to the above amount of carrier and emulsifier To obtain an emulsion. A predetermined amount of this emulsion is diluted with water to prepare a test drug.

Test method: In a greenhouse, various seeds of barnyard grass and barnyard grass were sown and covered on the surface of a 120 cm ² pot filled with field soil, and a predetermined amount of the above-mentioned drug was evenly applied to the soil surface of each test pot. . Four weeks after spraying, the degree of herbicidal effect was examined. The herbicidal effect was evaluated as 100% when completely killed, and 0% when equivalent to a non-treated section.

Result: Compound No. 1, 2, 6, 14, 3
0, 43, 57, 65 and 77 are 1 as the amount of the active ingredient.
The target weed was killed 100% at an application rate of kg / ha.

Test Example 2 : Test of post-emergence foliage treatment on field weeds Test method: 120 cm of field soil packed in a greenhouse
^{In two} pots, seeds of barnyard grass and barnyardgrass were sowed and covered, and 10 days after sowing and covering (weeds averaged 2 leaf stage), the above Test Example 1 was used.
A predetermined amount of the drug prepared in the same manner as in Example 1 was uniformly applied to the foliage of the test plant in each test pot. Three weeks after spraying, the degree of herbicidal effect was examined.

Results: Compound Nos. 1, 15, 57, 65,
Nos. 73 and 85 killed the target weeds by 90% or more at an application rate of 2 kg / ha as an active ingredient.

Formulation Example 1 (Granules) 25 parts of water was added to a mixture of 10 parts of Compound No. 1, 30 parts of bentonite (montmorillonite), 58 parts of talc (talc) and 2 parts of ligninsulfonate, and kneaded well. ,
Granules of 10 to 40 mesh are formed by an extruder and dried at 40 to 50 ° C to obtain granules.

Formulation Example 2 (Granules) 95 parts of clay mineral particles having a particle size distribution of 0.2 to 2 mm are put in a rotary mixer, and while rotating, 5 parts of Compound No. 145 are sprayed together with a liquid diluent, and the mixture is evenly sprayed. After being squeezed, 40 ~ 5
Dry at 0 ° C. to make granules.

Formulation Example 3 (Emulsion) 30 parts of Compound No. 1, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to form an emulsion.

Formulation Example 4 (Wettable powder) 15 parts of Compound No. 15, a mixture of white carbon (hydrous amorphous silicon oxide fine powder) and powdered clay (1:
5) 80 parts, sodium alkylbenzene sulfonate 2
Parts and 3 parts of sodium alkylnaphthalenesulfonate formalin condensate are pulverized and mixed to obtain a wettable powder.

Formulation Example 5 (Hydrated granules) Compound No. 57 (20 parts), ligninsulfonic acid sodium salt (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) were thoroughly mixed, and water was added. Extrude and dry with a screen to obtain hydrated granules.

[0164]

The novel herbicidal 1-substituted methyltetrazolinone derivative of the present invention can be easily synthesized by a general production method as shown in the Examples, and exhibits an effective action as a herbicide. .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshiko Kyo 934-7 Kamitani, Oyama City, Tochigi Prefecture (72) Inventor Chieko Ueno 258-1, Inabago, Oyama City, Tochigi Prefecture

Claims (5)

[Claims] (1) Formula (1) Wherein R ¹ has ¹ to 3 heteroatoms arbitrarily selected from the group consisting of N, O and S, optionally substituted with halogen and / or C _1-4 alkyl.
Or an oxiran-2-yl, optionally substituted chloro-substituted pyridyl or C _1-4 alkyl-S (O) m-, wherein m is 0, 1 or 2 Or a C _3-6 alicyclic hydrocarbon group, and R ² and R
³ each independently represents C _1-6 alkyl, C _3-7 cycloalkyl or optionally substituted phenyl,
Alternatively, R ² and R ³ together with the N atom to which they are attached may form an optionally substituted ring, R ⁴ represents a hydrogen atom or methyl, and n is 0 or 1-substituted methyltetrazolinone represented by 1. 2. R ¹ has one or two N atoms and one O or one S atom, has two N atoms, or has one N or O atom. 5 which is optionally substituted with chloro and / or methyl
R ² represents a membered heterocyclic group, or represents oxiran-2-yl, optionally substituted chloro-substituted pyridyl, C _1-3 alkylthio, methylsulfinyl, methylsulfonyl, cyclopropyl, cyclopentenyl or cyclohexyl; And R ³ are each independently C _1-4 alkyl, C _5-6 cycloalkyl, optionally substituted phenyl, wherein the substituent is halogen or C _1-4 alkyl.
Or wherein R ² and R ³ together with the N atom to which they are attached are optionally substituted 1,2-
Dihydroquinolin-1-yl or 1,2,3,4-tetrahydroquinolin-1-yl, wherein the substituent is methyl or fluoro, R ⁴ represents a hydrogen atom and n The compound according to claim 1, wherein represents 0 or 1. 3. R ¹ is isoxazolyl, pyrazolyl,
1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, thienyl or furyl, these groups being optionally substituted with chloro and / or methyl, or oxiran-2-yl, Represents 3-pyridyl, 6-chloro-3-pyridyl, methylthio, n-propylthio, isopropylthio, methylsulfinyl, methylsulfonyl, cyclopropyl, cyclopentenyl or cyclohexyl, wherein R ² and R ³ each independently represent C _1-3 Represents alkyl, cyclohexyl or optionally substituted phenyl, wherein the substituent is fluoro, chloro, bromo or methyl, or R ² and R ³ are the N
Together with the atom, 6-fluoro-2,2-dimethyl-1,
2,3,4-tetrahydroquinolin-1-yl, 2-methyl-
1,2,3,4-tetrahydroquinolin-1-yl, 2,2-dimethyl-1,2-dihydroquinolin-1-yl, 6-fluoro
-2,2-dimethyl-1,2-dihydroquinolin-1-yl or 2,2-dimethyl-1,2,3,4-tetrahydroquinoline-1
A compound according to claim 1, wherein R ⁴ represents a hydrogen atom and n represents 0 or 1. 4. An agricultural chemical comprising the compound according to claim 1 as an active ingredient. 5. A compound of the formula Wherein R ¹ , R ⁴ and n have the same meaning as described in claim 1.