JPH11228567A - Substituted thiophene derivative and plant disease-controlling agent containing the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide new compound that has high controlling effect against plant diseases as rice blast, rust and the like with increased labor saving and safety to environments and is useful as a plant diseases-controlling agent. SOLUTION: This compound is represented by formula I [R is a 3-10C cycloalkyl in which the positions other than 2 are substituted with one or more 1-4C alkyls; Ar is a heterocyclic group of formula II (R1 is CF3 or the like; R2 is CF3 or the like) or the like], typically N- 2-[3-methyl-cyclopentyl)-3- trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide. the compound of formula I is prepared by reaction of a substituted aminothiophene of formula III [2-(3-methylcyclopentyl)-3-thienylamine or the like] with a carboxylic halide of the formula; ArCo-X (X is Al or the like) [3-trifluoromethyl-1- methylpyrazole-4-carboxylic acid chloride] in a melted state or in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel substituted thiophene derivative and a plant disease controlling agent containing the same as an active ingredient.

[0002]

2. Description of the Related Art Many aromatic anilide derivatives having a bactericidal activity have been known. Recently, for example, JP-A-5-221994 (European Patent Publication No. 545099) and JP-A-6-1998
No. 03 (EP-A-589301) describes that carboxylic acid anilide derivatives having various substituents at the 2-position of aniline are effective against gray mold. No. 5,498,624.
It is known that a pyrazole carboxylic acid anilide derivative having a cycloalkyl group or cycloalkenyl at the 2-position of the aniline ring has an effect on gray mold and powdery mildew in Japanese Patent Application Laid-Open No. 7-501549. I have.

On the other hand, Japanese Patent Application Laid-Open No. 9-235282 (EP-A-737682) describes that various substituted thiophene derivatives are effective for controlling plant diseases. In the present invention, a cycloalkyl group is contained as a substituent of thiophene, but only an unsubstituted cycloalkyl group or a cycloalkyl group alkyl-substituted at the 2-position is described, and other positions are described. Are not shown.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a controlling agent having a high controlling effect on various plant diseases, thereby saving labor and improving environmental safety.

[0005]

Means for Solving the Problems The present inventors have conducted research with an interest in the physiological activities possessed by various heterocyclic amine derivatives. Among them, in the 2-cycloalkyl-3-thiophenamine derivative, a compound in which an alkyl or haloalkyl group having 1 to 4 carbon atoms is introduced at a position other than the 2-position of the cycloalkyl group can be used for various plant diseases, particularly, rice. The present inventors have found that they have a high control effect against gray blast and powdery mildew in addition to blast and rust, and thus meet the above-mentioned problems, and thus completed the present invention.

That is, the present invention relates to a compound represented by the general formula (1):

[0007]

Embedded image [Wherein, R is a cycloalkyl group having 3 to 10 carbon atoms, and these groups are each substituted with at least one or more alkyl or haloalkyl groups having 1 to 4 carbon atoms at positions other than the 2-position. , Ar represents the following (A1) to (A12)

[0008]

Embedded image (Wherein, R 1 is CF ₃ , CHF ₂ , Me, an Et group or a halogen atom, and R 2 is CF ₃ , Me, NH ₂ , OMe
R3 is Me, OM
e, hydrogen or a halogen atom, and R4 is Me, E
t is a hydrogen atom or a halogen atom, and n is an integer of 0 to 2), provided that when Ar is (A9), (A10) or (A11), R1 Is not a halogen atom] and a plant disease control agent containing the derivative as an active ingredient.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The substituent R of the thiophene derivative represented by the general formula (1) of the present invention specifically has at least one carbon atom at a position other than the 2-position of a cycloalkyl group. A cycloalkyl group having 3 to 10 carbon atoms substituted with 1 to 4 alkyl or haloalkyl groups, for example, 3-methylcyclopentyl, 4-ethylcyclopentyl, 3-propylcyclopentyl, 3-methylcyclohexyl, 3-ethylcyclohexyl, 4-methylcyclohexyl, 3-methylcycloheptyl, 4-butylcycloheptyl, 3-methylcyclooctyl, 4-methylcyclononyl, 4-trifluoromethylcyclohexyl and the like.

The thiophene represented by the general formula (1) of the present invention
Specifically, Ar at the 4-position is CF at position 4._Three, CH
F_Two, Me, an Et group or a halogen atom, and the 2-position is
Hydrogen atom, Me, CF_Three, Amino group or halogen atom
5-thiazolyl group such as 2-methyl-4-tri
Fluoromethyl-5-thiazolyl group, 2-methyl-4-
Difluoromethyl-5-thiazolyl group, 2,4-dimethyl
Ru-5-thiazolyl group, 2-methyl-4-iodo-5
Thiazolyl group, 2-chloro-4-methyl-5-thiazoli
Group, 4-methyl-5-thiazolyl group, etc .;
F_Three, CHF_Two, Me, Et group or halogen atom substituted
And a hydrogen, halogen atom, Me group or methoxy at the 5-position
A substituted 1-methyl-4-pyrazolyl group, for example 1
-Methyl-3-difluoromethyl-4-pyrazolyl group,
1-methyl-5-chloro-3-trifluoromethyl-4
-Pyrazolyl group, 1-methyl-3-iodo-4-pyrazo
Ryl group, 1,5-dimethyl-3-trifluoromethyl-
4-pyrazolyl group, etc .; CF at the 2-position _Three, CHF_Two, Me, E
t group or halogen atom substituted, methyl group at 5 position
An optionally substituted 3-furyl group, for example, 2-methyl-3
-Furyl group, 2,5-dimethyl-3-furyl group, etc .; 3-position
To CF_Three, CHF_Two, Me, an Et group or a halogen atom
2-thiene, which may be substituted with a methyl group at the 5-position
Nyl group, for example, 3-methyl-2-thienyl group, 3,5-
Dimethyl-2-thienyl group; CF at the 2-position_Three, CHF_Two,
Phenyl substituted by Me, Et group or halogen atom
Group; CF at the 2-position_Three, CHF_Two, Me, Et group or halogen
A nicotinyl group substituted by a chloro atom; 3-chloro-2-pyra
Dinyl group; CF at the 4-position_Three, CHF_Two, Me, Et groups or
A 3-thienyl group substituted with a halogen atom, for example, 4-methyl
Tyl-3-thienyl group, 4-iodo-3-thienyl group
Etc .; CF in 3rd place_Three, CHF_Two, Me, Et groups substituted
3,4-dihydro-2H-pyran-5-yl group, for example
For example, 6-methyl-3,4-dihydro-2H-pyran-5
-Yl group; CF at the 6-position_Three, CHF_Two, Me, Et groups are substituted
2,3-dihydro-1,4-oxathiin-5-i
For example, 6-methyl-2,3-dihydro-1,4
-Oxathiin-5-yl group; CF at the 6-position_Three, CHF_Two,
2,3-dihydro-1,4-O substituted with Me, Et groups
A xathin-4-oxide-5-yl group, for example, 6-
Methyl-2,3-dihydro-1,4-oxathiin-4
-Oxide-5-yl group; CF at the 6-position_Three, CHF_Two, M
e, 2,3-dihydro-1,4-oxo substituted with an Et group
Satiin-4,4-dioxide-5-yl group, for example,
6-methyl-2,3-dihydro-1,4-oxathiin
-4,4-dioxide-5-yl group; CF at the 5-position_Three, C
HF_Two, Me, Et-substituted 2,3-dihydrofura
N-4-yl group, for example, 5-methyl-2,3-dihydrid
Rofuran-4-yl group; CF at the 3-position_Three, CHF_Two, Me,
Isothiazole substituted with an Et group or a halogen atom
4-yl group, for example, 3-methylisothiazole-4-
Yl group, 3-trifluoromethylisothiazole-4-
Yl group, etc., and particularly preferably 1-methyl
-3-trifluoromethyl-4-pyrazolyl group.

The substituted thiophene derivative represented by the general formula (1) of the present invention is a novel compound, and is obtained by a method similar to the known method shown in the following reaction formula (Formula 5).
And a carboxylic acid halide represented by the general formula (3) in a molten state or in a solvent.

[0012]

Embedded image (In the formula, R and Ar represent the above-mentioned meanings, and X represents a chlorine atom, a bromine atom, or an iodine atom.) The solvent used in this reaction may be any solvent that is inert to the reaction. Aliphatic hydrocarbons such as water, hexane and petroleum ether; aromatics such as benzene, toluene, chlorobenzene and anisole; ethers such as dioxane, tetrahydrofuran and diethyl ether; nitriles such as acetonitrile and propionitrile; Esters of dichloromethane; chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane; aprotic solvents such as dimethylformamide and dimethylsulfoxide; and mixed solvents thereof are also used.

The present reaction may be carried out in the presence of a base. Examples of the base include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide; Oxides of alkali metals and alkaline earth metals such as magnesium; hydrides of alkali metals and alkaline earth metals such as sodium hydride and calcium hydride; amides of alkali metals such as lithium amide and sodium amide; sodium carbonate and carbonic acid Carbonates of metals and alkaline earth metals such as potassium, calcium carbonate and magnesium carbonate; hydrogen carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and potassium hydrogen carbonate; methyllithium, butyllithium, phenyllithium, methyl Alkaline such as magnesium chloride Metal alkyls; alkoxides of alkali metals and alkaline earth metals such as sodium methoxide, sodium ethoxide, potassium-t-butoxide, and dimethoxymagnesium; triethylamine, pyridine, N, N-dimethylaniline, N-methylpiperidine, lutidine, -Various organic bases such as dimethylaminopyridine, and particularly preferred are triethylamine and pyridine. The use amount of these bases is not particularly limited, but is preferably from 5 mol% to 2 mol% based on the carboxylic acid halide represented by the general formula (3).
Used in 0 mol% excess.

The substituted aminothiophenes represented by the above formula (2) and the carboxylic acid halides represented by the general formula (3) are generally used in an equimolar amount. On the other hand, it may be used in a molar excess of 1 to 20 mol%. The reaction temperature is generally -20 to 150C, preferably 0 to 40C. The reaction time is not particularly limited, but is usually 30 minutes to 5 hours.

Next, a method for synthesizing the compound represented by the formula (2), which is an intermediate of the present invention, will be described. The starting material of the present invention, 2- (alkyl-substituted cycloalkyl) -3-aminothiophene, has been described in G.I. Bartoli et al. (J. Org. Chem., Vol 45 ,
p522 (1980)), the reaction of 3-nitrothiophene with a Grignard reagent followed by DDQ (2,3-dichloro-
5,6-dicyano-1,4-benzoquinone) or potassium permanganate to form a nitro form, which is then reduced with stannous chloride or iron / hydrochloric acid. The method is not limited.

The compound of the present invention represented by the general formula (1),
And a plant disease controlling agent containing it as an active ingredient,
Gray mold of green beans, cucumber, tomato, strawberry, grape, potato, soybean, cabbage, eggplant, lettuce
( Botrytis cinerea ), powdery mildew of cucumber ( Sphaerothec
a fuliginea ), as well as wheat rust ( Puccinia striif)
ormis ; P. graminis ; P. recondita ; P. hordei) and rice blast ( Pyriculariaoryzae ). In addition, these include strawberry powdery mildew ( Sphaerotheca humuli ) and wheat powdery mildew ( Erysip
he graminis f.sp. hordei; f.sp. tritici) , tomato powdery mildew (Erysiphe cichoracearum), grape powdery mildew (Uncinula necator), grape rust (Phakopsora am
pelopsidis ), Sclerotinia sc
lerotiorum ), rice sheath blight ( Rhizoctonia solani ), apple scab ( Venturia inaequalis ), spot leaf spot ( Alte
rnaria mali ), scab ( Gymnosporangium yamadae ), Monilia disease ( Sclerotinia mali ), pear black spot ( Alternari
a kikuchiana ), scab ( Venturia nashicola ), scab
( Gymnosporangium haraeanum ), peach rot disease ( Scleroti
nia cinerea ), green onion rust ( Puccinia allii ), rice sesame leaf blight ( Cochliobolus miyabeanus ), stupid seedling disease ( Gibb
erella fujikuroi ), leaf spot disease ( Pyrenophora graminea ),
Nettle spot (Pyrenophora teres ), Fusarium head blight ( Gibberella zea)
e ), snow rot ( Typhula sp .; Micronectriella nivalis ),
Naked smut ( Ustilago tritic i; U. nuda ), eye spot disease ( Pseudoc
ercosporella herpotrichoides ), scald disease ( Rhynchospori )
um secalis ), leaf blight ( Septoria tritici ), blight ( Lept
osphaeria nodorum ), black rot ( Elsinoe ampelina ), late rot ( Glomerella cingulata ), citrus black spot ( Diapo
rthe citri ), apple powdery mildew ( Podosphaera leucot)
richa ), rot ( Valsa mali ), pear ring spot ( Physalo)
spora piricola ), peach scab ( Cladosporium carpoph)
. ilum), Phomopsis rot (Phomopsis sp), oysters of anthracnose (Gloeosporium kaki), deciduous disease (Cercospora kaki; M
ycosphaerella nawae ), powdery mildew ( Phyllactinia kaki
kora ), cucumber anthracnose ( colletotrichum lagenarium ),
Vine blight ( Mycosphaerella melonis ), tomato ring spot ( A
lternaria solani ), leaf mold ( Cladosporium fulvam ),
Black spot of cruciferous vegetables ( Alternaria japonica ), white spot ( Cerocosporella barassicae ), black spot of green onion ( Altern
aria porri ), soybean purpura ( Cercospora kikukuchi)
i ), black spot ( Elsinoe glycinnes ), black spot ( Diaporthe
phaseololum ), bean anthracnose ( colletotrichum lind
emuthianum ), peanut black spot ( Mycosphaerella per
sonatum ), brown spot ( Cercospora arachidicola ), pea powdery mildew ( Erysiphe pisi ), potato summer blight
( Alternaria solani ), Black bruise ( Rhizoctonia solan)
i ), tea net blast ( Exobasidium reticulatum ), scab ( Elsinoe leucospila ), anthracnose ( Colletotrichum the
ae-sinensis) , tobacco scab ( Alternaria longipe)
s ), powdery mildew ( Erysiphe cichoracearum ), anthracnose ( Col )
letotrichum tabacum ), brown spot of sugar beet ( Cercospora
beticola ), rose scab ( Diplocarponrosae ), powdery mildew ( Sphaerotheca pannosa ), chrysanthemum brown spot ( Septoria
chrysanthemi - indici ), white rust ( Puccinia horiana ),
It may also be effective against diseases such as Chinese cabbage white spot ( Cercospora brassiicae ) and carrot black leaf blight ( Alternaria dauci ).

When the compound represented by the general formula (1) of the present invention is used as a plant disease controlling agent, the drug substance may be used as it is for the plant to be treated, but it is generally an inert liquid. It is mixed with a carrier or a solid carrier and used as powders, wettable powders, flowables, emulsions, granules and other commonly used forms of preparations which are commonly used. If necessary for the preparation, an auxiliary agent can be added.

The carrier as used herein refers to a synthetic or natural inorganic or organic substance incorporated to help the active ingredient reach the site to be treated and to facilitate storage, transport, and handling of the active ingredient compound. Means As the carrier, any solid or liquid carrier can be used as long as it is generally used for agricultural and horticultural medicines, and it is not limited to a specific one.

For example, solid carriers include clays such as montmorillonite and kaolinite; inorganic substances such as diatomaceous earth, terra alba, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate; soy flour, sawdust, flour and the like. Plant organic substances and urea.

As the liquid carrier, toluene, xylene,
Aromatic hydrocarbons such as cumene; paraffinic hydrocarbons such as kerosene and mineral oil; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and diethylene glycol dimethyl ether; alcohols such as methanol, ethanol, propanol and ethylene glycol; Examples include aprotic solvents such as dimethylformamide and dimethylsulfoxide, and water.

Further, in order to enhance the efficacy of the compound of the present invention, the plant disease controlling agent of the present invention may be used alone or in combination according to the purpose, taking into account the dosage form of the preparation, application scene, etc., as follows. Various auxiliaries can be added. Examples of the auxiliary include surfactants, binders (eg, ligninsulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, sodium CMC, etc.) and stabilizers (eg, phenol for antioxidant use) which are commonly used in plant disease control agents. Phosphates, light stabilizers, etc., as pH adjusters, etc., can be used alone or in combination as needed. Further, depending on the case, an industrial bactericide, a bactericidal / antifungal agent or the like may be added for bactericidal / fungicidal purposes.

The adjuvant will be described in more detail. Auxiliaries include lignin sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl phosphate for the purpose of emulsification, dispersion, spreading, wetting, bonding, stabilization, etc. Anionic surfactants such as salts; polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers, polyoxyalkylene alkylamines, polyoxyalkylene alkylamides, polyoxyalkylene alkylamides, polyoxyalkylene alkylthioethers, polyoxyalkylene fatty acids Ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxypropylene polyoxyethylene block polymer Calcium stearate, lubricants such as wax; stabilizers isopropyl hydroperoxide diene phosphate, etc., other cellulose, non-ionic surfactant
Carboxymethyl cellulose, casein, gum arabic and the like can be mentioned. However, these components are not limited to those described above.

The content of the compound represented by the general formula (1) in the plant disease controlling agent according to the present invention varies depending on the form of preparation, but usually 0.05 to 20% by weight in powder.
0.1-80% by weight for wettable powders, 0.1-20% for granules
% By weight, 1 to 50% by weight in the emulsion, 1 to 50% by weight in the flowable preparation, 1 to 80% by weight in the dry flowable preparation, preferably 0.5 to 5% by weight in the powder,
5 to 80% by weight for wettable powders, 0.5 to 8% by weight for granules, 5 to 20% by weight for emulsions, 5 to 20% for flowable preparations
50% by weight and 5 to 50% by weight for dry flowable formulations. The content of the auxiliary agent is 0 to 80% by weight,
The content of the carrier is an amount obtained by subtracting the contents of the active ingredient compound and the auxiliary from 100% by weight.

The method for applying the plant disease controlling agent of the present invention includes seed disinfection, foliage application, and the like, and any application method usually used by those skilled in the art can exert sufficient effects. The application rate and application concentration vary depending on the target crop, the target disease, the degree of occurrence of the disease, the dosage form of the compound, the application method and various environmental conditions, etc., but when sprayed, the active ingredient amount is 50 to 1,000 g per hectare. Is suitable, desirably from 100 to 500 g per hectare. When a wettable powder, a flowable or an emulsion is diluted with water and sprayed, the dilution ratio is 200 to 20,000.
Double is appropriate, preferably 1,000 to 5,000.

The plant disease controlling agent of the present invention may be used in combination with other pesticides such as fungicides, insecticides, herbicides and plant growth regulators, soil conditioners or fertilizers, or in combination with these. Formulations are also possible. Examples of the disinfectant include azole disinfectants such as triadimefon, hexaconazole, prochloraz, and triflumizole; acylalanine disinfectants such as metalaxyl and oxadixyl; benzimidazole disinfectants such as thiophanate methyl and benomyl; manzeb and the like Dithiocarbamate fungicides and tetrachloroisophthalonitrile, sulfur and the like.Examples of insecticides include, for example, fenitrothion, diazinon, pyridafenthion, chlorpyrifos, marathon,
Fentoate, dimethoate, methylthiometon, prothiophos, DDVP, acephate, salicion, E
Phosphorus insecticides such as PN; NAC, MTMC, BPMC,
Examples include, but are not limited to, carbamate insecticides such as pirimicarb, carbosurphan, mesomil and the like and pyrethroid insecticides such as etofenprox, permethrin, fenvalerate and the like.

[0026]

The compounds of the present invention will be described more specifically with reference to the following examples. Example 1 N- {2- (3-methylcyclopentyl)-
Synthesis of 3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 1) Charge 0.48 g of 2- (3-methylcyclopentyl) -3-thienylamine to 3 ml of pyridine. Then, 0.56 g of 3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid chloride was added dropwise at room temperature. After stirring at room temperature for 1 hour, the mixture was discharged into 5% aqueous hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with 5% aqueous hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate.
After evaporating the solvent under reduced pressure using an evaporator, the residue was sludged with n-hexane to obtain 0.71 g of the desired product (yield 75%).
%) As colorless crystals. Melting point: 121.5-124.4 ° C. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.03 (1.5 H, d, J =
6.6), 1.07 (1.5H, d, J = 6.66), 1.21-2.26 (1H, m), 1.65-2.31
(6H, m), 3.18-3.42 (1H, m), 3.99 (3H, s), 7.07-7.09 (1H, m),
7.46-7.51 (1H, m), 7.58 (1H, brs), 8.05 (1H, s)

Example 2 Synthesis of N- {2- (3-methylcyclohexyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 3) 2- (3 1.08 g of -methylcyclohexyl) -3-thienylamine was charged into 5 ml of pyridine, and 1.18 g of 3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid chloride was added dropwise at room temperature. After stirring at room temperature for 1 hour, the mixture was discharged into 5% aqueous hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with 5% aqueous hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate.
After evaporating the solvent under reduced pressure by an evaporator, the residue was purified by silica gel chromatography (eluent: n-hexane: ethyl acetate = 6: 4) to obtain 1.28 g of the desired product (yield 7).
1%) as colorless crystals. Melting point: 93.4-103.5 ° C. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.80-1.13 (1H,
m), 0.93 (1.5H, d, J = 6.6), 1.02 (1.5H, d, J = 6.6), 1.29-2.09
(8H, m), 2.65-2.85 (0.5H, m), 3.08-3.17 (0.5H, m), 3.99 (3
H, s), 7.10-7.13 (1H, m), 7.49-7.52 (1H, m), 7.59 (1H, brs),
8.06 (1H, s)

Example 3 Synthesis of N- {2- (4-methylcyclohexyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 9) , 2- (3-methylcyclopentyl)
The target product was obtained as crystals by using 2- (4-methylcyclohexyl) -3-thienylamine in place of -3-thienylamine. Melting point: 105.4-119.6 ° C. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.92 (1.5 H, d, J =
6.6), 1.02 (1.5H, d, J = 6.6), 1.07-2.08 (9H, m), 2.67-2.84
(0.5H, m), 3.08-3.18 (0.5H, m), 3.99 (3H, s), 7.10-7.13 (1
H, m), 7.49-7.53 (1H, m), 7.58 (1H, brs), 8.06 (1H, s)

Reference Example Reference Example 1 N- {2-cyclohexyl-3-thienyl}
-3-trifluoromethyl-1-methylpyrazole-4
Synthesis of Carboxamide (Compound No. 6) In Example 1, 2- (3-methylcyclopentyl)
2-cyclohexyl instead of -3-thienylamine
The desired product was obtained as crystals by using 3-thienylamine. Melting point: 128.7-129.5 ° C. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.22-1.49 (5H,
m), 1.72-1.94 (5H, m), 2.72-2.79 (1H, m), 3.99 (3H, s), 7.10
(1H, d, J = 5.1), 7.51 (1H, d, J = 5.1), 7.60 (1H, brs), 8.06 (1
H, s)

Reference Example 2 N- ｛2-cycloheptyl-3
Synthesis of -thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 7) In Example 1, 2- (3-methylcyclopentyl)
2-cycloheptyl instead of -3-thienylamine
The desired product was obtained as crystals by using 3-thienylamine. Melting point: 137.6-138.3 ° C. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.49-1.84 (10H,
m), 1.97-2.04 (2H, m), 2.93-3.01 (1H, m), 4.05 (3H, s), 7.09
(1H, d, J = 5.1), 7.46 (1H, d, J = 5.1), 7.56 (1H, brs), 8.06 (1
H, s)

Synthesis of Raw Materials and Intermediates Reference Example 3 3-methylcyclopentyl chloride 5 g of 3-methylcyclopentanol, calcium chloride 4
g was placed in 11 ml of concentrated hydrochloric acid, stirred at 100 ° C. for 9 hours, and then discharged into water. After extraction with ethyl ether, the organic layer was washed successively with a saturated aqueous solution of sodium hydrogen carbonate and a saturated saline solution, and dried overnight with calcium chloride. After evaporating the solvent under reduced pressure using an evaporator, the residue was distilled under reduced pressure to obtain 2.12 g (yield 36%) of a target product as a colorless liquid. Boiling point: 68-73 ° C./110 mmHg ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.00-1.11 (3H,
m), 1.12-2.42 (7H, m), 4.25-4.47 (1H, m)

Reference Example 4 3-Methylcyclohexyl chloride 50 g of 3-methylcyclohexanol and 35.2 g of calcium chloride were charged into 160 ml of concentrated hydrochloric acid.
After heating and stirring for 6 hours, the mixture was discharged into water. After extraction with ethyl ether, the organic layer was washed successively with a saturated aqueous solution of sodium hydrogen carbonate and a saturated saline solution, and dried overnight with calcium chloride. After evaporating the solvent under reduced pressure by an evaporator, the residue was distilled under reduced pressure to obtain 31 g (yield 53%) of a target product as a colorless liquid. Boiling point: 90-93 ° C./90 mmHg ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.82-0.96 (3H,
m), 1.20-2.20 (9H, m), 3.78-3.92 (0.5H, m), 4.40-4.52 (0.
5, m)

Reference Example 5 2- (3-methylcyclopentyl) -3-aminothiophene 1) 2- (3-methylcyclopentyl) -3-nitrothiophene Under a nitrogen atmosphere, 0.41 g of magnesium was charged into 20 ml of ethyl ether. Thereafter, 2.0 g of 3-methylcyclopentyl chloride was added dropwise under reflux to prepare a Grignard reagent. After adding 30 ml of tetrahydrofuran to dilute the mixture, the mixture was cooled to −60 ° C., and a solution of 1.09 g of 3-nitrothiophene in 5 ml of tetrahydrofuran was added dropwise while keeping the internal temperature at −50 ° C. or lower. After stirring at −50 ° C. for 10 minutes, DDQ (1.92 g) in tetrahydrofuran (10 ml)
The solution was added dropwise while maintaining the internal temperature at -45 ° C or less,
Stirred at 30 ° C. for 30 minutes. After discharging into a saturated aqueous ammonium chloride solution, celite was added and the mixture was filtered, and the filtrate was extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (elution solvent: n-hexane: toluene = 10: 1) to obtain 0.67 g (yield 38%) of a target product as a yellow oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.05-1.09 (3H,
m), 1.20-2.43 (7H, m), 4.05-4.28 (1H, m), 7.03 (1H, d, J = 5.
9), 7.56 (1H, d, J = 5.9)

2) 2- (3-methylcyclopentyl)-
3-aminothiophene 0.67 g of the above nitro compound and 2.41 g of stannous chloride
After charging into 3 ml of ethyl alcohol, 3 ml of concentrated hydrochloric acid was added.
Then, the mixture was heated and stirred at 60-70 ° C for 1 hour. Saturated bicarbonate
After discharging into sodium aqueous solution, add celite and filter,
The filtrate was extracted with ethyl acetate. Wash the organic layer with saturated saline
After the purification, it was dried with anhydrous sodium sulfate. The filtrate is concentrated under reduced pressure
Then, the desired product was combined with 0.48 g (83% yield) of brown oil.
I got it. ¹ NMR (270MHz, CDCl_Three, δppm, J: Hz): 1.03 (1.5H, d, J =
6.6), 1.06 (1.5H, d, J = 6.6), 1.15-2.30 (7H, m), 3.10-3.48
(3H, m), 6.56 (1H, d, J = 5.1), 6.90-6.93 (1H, m)

Reference Example 6 2- (3-methylcyclohexyl) -3-aminothiophene 1) 2- (3-methylcyclohexyl) -3-nitrothiophene 1.2 g of magnesium was charged into 40 ml of ethyl ether under a nitrogen atmosphere. Thereafter, 6.2 g of 3-methylcyclohexyl chloride was added dropwise under reflux to prepare a Grignard reagent. To this, 50 ml of tetrahydrofuran was added for dilution, and the mixture was cooled to -60 ° C, and a solution of 3.0 g of 3-nitrothiophene in 10 ml of tetrahydrofuran was added dropwise while keeping the internal temperature at -50 ° C or lower. After stirring at −50 ° C. for 10 minutes, a solution of 5.29 g of DDQ in 20 ml of tetrahydrofuran was added dropwise while maintaining the internal temperature at −45 ° C. or lower.
For 1 hour. After discharging into a saturated aqueous ammonium chloride solution, celite was added and the mixture was filtered, and the filtrate was extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: n-hexane: toluene = 12: 1) to obtain 2.6 g of the desired product (yield: 50).
%) As a yellow oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.95 (1.5 H, d, J =
7.3), 1.10 (1.5H, d, J = 7.3), 1.18-1.90 (7H, m), 1.98-2.12
(2H, m), 3.69-3.84 (0.5H, m), 3.99-4.07 (0.5H, m), 7.05-7.
10 (1H, m), 7.54-7.59 (1H, m)

2) 2- (3-methylcyclohexyl)-
3-Aminothiophene 2.0 g of the above nitro compound and 6.7 g of stannous chloride were charged into 8 ml of ethyl alcohol, and 8 ml of concentrated hydrochloric acid was added.
The mixture was heated and stirred at 0-70 ° C for 1 hour. After discharging into a saturated aqueous solution of sodium hydrogen carbonate, celite was added and the mixture was filtered, and the filtrate was extracted with ethyl acetate. After washing the organic layer with saturated saline,
Dry over anhydrous sodium sulfate. The filtrate was concentrated under reduced pressure to obtain 1.73 g (yield: quantitative) of a target product as a brown oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.92 (1.5 H, d, J =
6.6), 1.03 (1.5H, d, J = 6.6), 1.30-2.05 (9H, m), 2.63-2.74
(0.5H, m), 2.97-3.06 (0.5H, m), 3.36 (2H, brs), 6.54-6.58
(1H, m), 6.93-6.95 (1H, m)

Reference Example 7 2- (4-methylcyclohexyl) -3-aminothiophene 1) 2- (4-methylcyclohexyl) -3-nitrothiophene In Example 1) of Example 5, instead of 3-methylcyclopentyl chloride, The target product was obtained as an oil by using 4-methylcyclohexyl chloride. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.93-1.07 (3H,
m), 1.18-1.90 (7H, m), 2.03-2.12 (2H, m), 3.64-4.09 (1H,
m), 7.05-7.09 (1H, m), 7.55-7.57 (1H, m)

2) 2- (4-methylcyclohexyl)-
3-Aminothiophene The target compound was obtained as an oil by using the above nitro compound in place of 2- (3-methylcyclopentyl) -3-nitrothiophene in 2) of Reference Example 5). ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 0.92 (1.5 H, d, J =
6.6), 1.02 (1.5H, d, J = 6.6), 1.32-1.96 (9H, m), 2.54-3.06
(1H, m), 3.36 (2H, brs), 6.56-6.58 (1H, m), 6.93-6.96 (1H,
m)

Reference Example 8 2-Cyclohexyl-3-aminothiophene 1) 2-Cyclohexyl-3-nitrothiophene In 1) of Reference Example 5, the intended product was obtained by using cyclohexyl chloride instead of 3-methylcyclopentyl chloride. Was obtained as a yellow oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.22-1.55 (5H,
m), 1.74-1.89 (3H, m), 2.08-2.12 (2H, m), 3.70-3.80 (1H,
m), 7.06 (1H, d, J = 5.1), 7.55 (1H, d, J = 5.1)

2) 2-Cyclohexyl-3-aminothiophene In 2) of Reference Example 5, the above-mentioned nitro compound is used in place of 2- (3-methylcyclopentyl) -3-nitrothiophene to obtain the desired product. Obtained as a yellow oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.21-1.97 (10H,
m), 2.60-2.69 (1H, m), 3.36 (2H, brs), 6.57 (1H, d, J = 5.1),
6.93 (1H, d, J = 5.1)

REFERENCE EXAMPLE 9 2-Cycloheptyl-3-aminothiophene 1) 2-Cycloheptyl-3-nitrothiophene In the same manner as in 1) of Reference Example 5, but using cycloheptyl chloride instead of 3-methylcyclopentyl chloride. The desired product was obtained as an oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.60-1.85 (10H,
m), 2.05-2.14 (2H, m), 3.91-3.98 (1H, m), 7.05 (1H, d, J = 5.
1), 7.54 (1H, d, J = 5.1)

2) 2-Cycloheptyl-3-aminothiophene By using the above nitro compound in place of 2- (3-methylcyclopentyl) -3-nitrothiophene in 2) of Reference Example 5, the desired product is obtained. Was obtained as an oil. ¹ NMR (270 MHz, CDCl ₃ , δ ppm, J: Hz): 1.46-1.82 (10H,
m), 1.98-2.04 (2H, m), 2.77-2.90 (1H, m), 3.45 (2H, brs), 6.
55 (1H, d, J = 5.1), 6.91 (1H, d, J = 5.1) The following Tables 1-2 (Tables 1-2) show the compounds represented by the general formula (1).

[0043]

[Table 1]

[0044]

[Table 2]

Next, preparation examples and test examples of the plant disease controlling agent according to the present invention will be shown. Formulation Example Formulation Example 1 (Dust) 2 parts of Compound No. 1 and 98 parts of clay were uniformly mixed and pulverized to obtain a dust containing 2% of the active ingredient.

Formulation Example 2 (Wettable powder) 10 parts of the compound of Compound No. 3, 70 parts of kaolin, 18 parts of white carbon and 2 parts of calcium alkylbenzenesulfonate are uniformly mixed and pulverized to obtain a fine powder having a uniform composition. A wettable powder containing 10% of the component was obtained.

Formulation Example 3 (Wettable powder) 20 parts of the compound of Compound No. 1, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay are uniformly mixed and pulverized to obtain a fine composition having a uniform composition. A powdered wettable powder containing 20% of the active ingredient was obtained.

Formulation Example 4 (Wettable powder) 50 parts of compound No. 8, 1 part of sodium ligninsulfonate, 5 parts of white carbon and 44 parts of diatomaceous earth are mixed and pulverized to obtain a wettable powder containing 50% of an active ingredient. I got

Formulation Example 5 (floatable) 5 parts of Compound No. 3 and propylene glycol 7
Parts, 4 parts of sodium ligninsulfonate, 2 parts of sodium dioctylsulfosuccinate, and 82 parts of water were wet-pulverized with a sand grinder to obtain a flowable agent containing 5% of the active ingredient.

Formulation Example 6 (Flowable agent) 10 parts of Compound No. 9 and propylene glycol 7
Parts, 2 parts of sodium ligninsulfonate, 2 parts of dioctyl sulfosuccinate sodium salt, and 79 parts of water were wet-pulverized with a sand grinder to obtain a flowable agent containing 10% of the active ingredient.

Formulation Example 7 (Flourable) 25 parts of Compound No. 1 and propylene glycol 5
Parts, 5 parts of polyoxyethylene oleate, 5 parts of polyoxyethylene diallyl ether sulfate, 0.2 part of a silicon-based antifoaming agent, and 59.8 parts of water were wet-pulverized with a sand grinder to obtain 25% of an active ingredient. A flowable was obtained.

[Test Example] Test Example 1 Wheat Rust Control Test Wheat (cultivar: Norin 6) grown in a greenhouse in plastic pots having a diameter of 6 cm until the 1.5-leaf stage by 15 to 20 leaves.
No. 1), a wettable powder prepared according to Formulation Example 3 of the compound of the present invention was diluted to a predetermined concentration (concentration of active ingredient: 200 ppm), and 50 ml was sprayed per 3 pots. After the chemical solution was dried, euspores of wheat leaf rust ( Puccinia recondita ) were sprayed and kept in a humidified state for 2 days, and then transferred to a room at a temperature of 18 ° C. Ten days after inoculation, the area occupied by the leaf rust spot on the first leaf of wheat was investigated according to the following index to determine the degree of disease onset, and the control value was calculated according to the following formula. Results 3 to
The results are shown in Table 4 (Tables 3 and 4). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

Test Example 2 Rice Blast Control Test A rice (cultivar: Mangetsumochi) grown in a greenhouse in a plastic cup having a diameter of 7 cm (having no hole at the bottom) by 30 to 40 plants until the second leaf stage. The wettable powder prepared according to Formulation Example 3 was prepared by diluting the inventive compound and the control compound to a predetermined concentration (active ingredient concentration: 200 ppm) and sprayed 50 ml per 3 pots. After the drug solution dries, the rice blast fungus ( Pyricularia or
yzae ) (4 × 10 ⁵ / m)
l) by spray inoculation on the whole rice, temperature 25 ° C, humidity 95%
It was kept in the above artificial weather room for 7 days. 7 days after inoculation, rice 5
The number of lesions of rice blast per book was investigated according to the following index. The results are shown in Tables 3 and 4 (Tables 3 and 4). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

In Table 4, the control compounds 1 and 2 are as follows. Control Compound 1: Triadimefon, trade name = Bileton,
Chemical name = 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl)-
2-butanone control compound 2: tricyclazole, trade name = beam, chemical name = 5-methyl-1,2,4-triazolo [3,4-
b] Benzothiazole Compound numbers 6 to 8 and 10 in Table 3 are the compounds described in the above-mentioned JP-A-9-2352825.

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

Industrial Applicability The novel thiophene derivative represented by the general formula (1) of the present invention has a high control effect on various plant diseases, especially rice blast and rust, and is labor-saving and environmentally friendly. It is useful as a plant disease control agent by increasing the safety of the plant.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 43/56 A01N 43/56 A 43/60 43/60 43/78 43/78 B 43/80 102 43/80 102 C07D 409 / 12 213 C07D 409/12 213 231 231 241 241 307 307 307 309 309 411/12 411/12 417/12 333 417/12/12 333 (72) Inventor Kanji Tomiya 1144 Togo, Togo, Mobara City, Chiba Pref. 72) Inventor Yuji Yanase 1144 Togo, Mogo-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Hideo Kawashima 1144 Togo, Togo, Mobara-shi, Chiba Mitsui Chemicals Incorporated

Claims (6)

[Claims] (1) Formula (1) (Formula 1) [Wherein, R is a cycloalkyl group having 3 to 10 carbon atoms, and these groups are each substituted with at least one or more alkyl or haloalkyl groups having 1 to 4 carbon atoms at positions other than the 2-position. , Ar are represented by the following formulas (A1) to (A12). (Wherein, R 1 is CF ₃ , CHF ₂ , Me, an Et group or a halogen atom, and R 2 is CF ₃ , Me, NH ₂ , OMe
R3 is Me, OM
e, hydrogen or a halogen atom, and R4 is Me, E
t is a hydrogen atom or a halogen atom, and n is an integer of 0 to 2), provided that when Ar is (A9), (A10) or (A11), R1 Is not a halogen atom].
2. The substituted thiophene derivative according to claim 1, wherein R is a 3-methylcycloalkyl group or a 4-methylcycloalkyl group. 3. The substituted thiophene derivative according to claim 2, wherein the cycloalkyl group is a cyclopentyl group or a cyclohexyl group. 4. The substituted thiophene derivative according to claim 1, wherein Ar is (A1), R 1 is CF ₃ or Me group, and R 2 is Me group. 5. The method according to claim 1, wherein Ar is (A2), R 1 is a CF ₃ or CHF ₂ group, and R 3 is a hydrogen atom.
4. The substituted thiophene derivative according to 3. 6. A plant disease controlling agent comprising the substituted thiophene derivative according to claim 1 as an active ingredient.