JP2002114776A - Benzothiophene derivative and herbicidal composition by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound hardly providing chemical damage to cultivated crops such as paddy rice, and capable of controlling a wide range of weeds with a small amount of the chemical, and further to provide a herbicidal composition by using the compound. SOLUTION: Thie compound is a benzothiophene derivative represented by general formula (I). The herbicidal composition contains the benzothiophene derivative as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel benzothiophene derivative and a herbicidal composition containing the benzothiophene derivative as an active ingredient. More specifically, the present invention relates to a benzothiophene derivative which is highly useful as a herbicide effective for field weeds and paddy weeds that inhibit the growth of cultivated plants, and particularly effective for paddy weeds, and a herbicide composition containing the same as an active ingredient.

[0002]

2. Description of the Related Art Herbicides are extremely important agents for saving labor for weed control and improving production of agricultural and horticultural crops.
Therefore, research and development of herbicides have been actively carried out for many years, and a wide variety of drugs have been put to practical use at present. However, even today, there is a demand for the development of new drugs with even more excellent herbicidal properties, especially those that can selectively control only the target weeds at low doses without causing phytotoxicity to field-cultivated crops and rice. It is rare. Certain types of triketone derivatives having a bicyclic benzoyl structure are known to be highly safe against field crops and have good herbicidal activity against field weeds. However, among the triketone derivatives having the bicyclic benzoyl structure, (2,3-dihydrobenzothiophen-5-yl) carbonyl-2,
There are few studies on 6-cyclohexanedione derivatives, and little is known about their herbicidal activity.

[0003] Japanese Patent No. 2579663 discloses a substituted cyclic dione compound as a herbicidally active compound.
The claims also encompass the (2,3-dihydrobenzothiophen-5-yl) carbonyl-2,6-cyclohexanedione derivative. However, in this patent, the above derivatives are not specifically described, nor are they exemplified, and therefore, of course, no mention is made of their herbicidal activity. In addition, the present inventors have proposed a (2,3-dihydrobenzothiophen-5-yl) carbonyl-2,6-dicyclohexanedione derivative having a herbicidal activity represented by the general formula (II):

[0004]

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(Wherein E is a 1,3-cyclohexanedione derivative-2-yl group, D is a substituent, R is a hydrogen atom or a lower alkyl group, and m is an integer of 0 to 2). Have been previously found (WO 00/20408). The compound represented by the general formula (II) has little phytotoxicity to cultivated crops, especially to rice, and can control a wide range of weeds at a low dose. It has been desired to develop a compound which has a wide herbicidal spectrum and can control a wide range of weeds at a low dose.

[0006]

Under such circumstances, the present invention can control a wide range of weeds at a low dose in such a manner that the phytotoxicity to cultivated crops, especially rice, etc. is extremely small, the herbicidal spectrum is wide, and a wide range of weeds is used. It is an object of the present invention to provide a novel compound and a herbicide composition containing the same as an active ingredient, particularly a herbicide composition for paddy rice.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object and found that (2,3-dihydrobenzothiophen-5-yl) carbonyl-2,2
A 6-cyclohexanedione derivatives, found that O at the 2-position of the benzothiophene ring, S, compounds in which an alkyl group is linked via a SO or SO ₂ may be adapted to that purpose. The present invention has been completed based on such findings. That is, the present invention provides a compound represented by the general formula (I):

[0008]

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(Wherein, R ^{1 to} R ⁶ each represent a hydrogen atom,
Halogen atom, alkyl group having 1 to 6 carbon atoms or 1 carbon atom
To haloalkyl groups, wherein two substituents selected from R ^{1 to} R ⁶ may be bonded to each other to form a bicichro ring together with the cyclohexene ring, and R ⁷ represents a substituent. It represents an alkyl group having 1 to 6 carbon atoms which may be present. Q is a hydroxyl group, a halogen atom, or an optionally substituted alkoxyl group having 1 to 6 carbon atoms,
6 alkylthio groups, alkylsulfinyl groups having 1 to 6 carbon atoms, alkylsulfonyl groups having 1 to 6 carbon atoms, phenoxy groups, phenylthio groups, phenylsulfinyl groups, phenylsulfonyl groups, dialkylamino groups having 2 to 12 carbon atoms, carbon atoms A 2 to 12-membered N-alkoxyalkylamino group, a 5- or 6-membered nitrogen-containing heterocyclic residue connected by a nitrogen atom or a 5- or 6-membered heterocyclic sulfide group, or a connection at the α-position Malonic ester residues,
A β-ketoester residue connected at the α-position or a β-diketone residue connected at the α-position is shown. X represents a halogen atom, a nitro group, a cyano group, R ⁸ , OR ⁸ , SR ⁸ , SO ₂ R ⁸ or NR ⁸ R ⁹ . R ⁸ and R ⁹ each represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, phenyl A benzyl group or NR
^{In 8} R ⁹ , R ⁸ and R ⁹ may be the same or different, and R ⁸ and R ⁹ may be bonded to each other to form a ring structure. Y is O, S, SO or SO
₂ , n represents 0, 1 or 2, and p represents 1 or 2. The present invention provides a benzothiophene derivative represented by the following formula: The present invention also provides a herbicidal composition comprising the above benzothiophene derivative as an active ingredient.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The benzothiophene derivative of the present invention has the general formula (I)

[0011]

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A compound having the chemical structure represented by In the general formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. here,
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group and various propyl groups, a butyl group, a pentyl group, A hexyl group. Various propyl, butyl, pentyl and hexyl groups include straight, branched or cyclic substituent isomers. Specific examples of the haloalkyl group having 1 to 6 carbon atoms include a haloalkyl group in which part or all of the hydrogen atoms of the above alkyl group are substituted with a halogen atom such as a chlorine atom, a fluorine atom, a bromine atom or an iodine atom; For example, chloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, 2-chloroethyl, 2-fluoroethyl, 3-chloropropyl, 3
-Fluoropropyl group and the like. This R ^{1 to} R ⁶
Is preferably a hydrogen atom. Further, two substituents selected from R ^{1 to} R ⁶ are bonded to each other to form a bicyclo ring such as bicyclo [3.
2.1] Octane or the like may be formed.

R ⁷ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include the aforementioned R ^{1 to} R ⁶
Among them, various groups exemplified in the description of the alkyl group having 1 to 6 carbon atoms, and the groups having a substituent can be given. Specifically, methyl, ethyl, isopropyl, propyl, 2-methoxyethyl, 2,2-dimethoxyethyl, 2-oxoethyl, 2-methoxyiminoethyl, 2-hydroxyiminoethyl, Examples thereof include a methoxycarbonylmethyl group, and among these, a methyl group, an ethyl group, a 2-methoxyethyl group,
-A methoxyiminoethyl group and a methoxycarbonylmethyl group are preferred.

Q represents a hydroxyl group, a halogen atom, or an optionally substituted alkoxyl group having 1 to 6 carbon atoms;
C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, phenoxy group, phenylthio group, phenylsulfinyl group, phenylsulfonyl group, C2-C12 dialkyl An amino group, an N-alkoxyalkylamino group having 2 to 12 carbon atoms, a 5- or 6-membered nitrogen-containing heterocyclic residue connected by a nitrogen atom, or a 5- or 6-membered heterocyclic sulfide group, or α A malonic ester residue connected at the α-position, a β-ketoester residue connected at the α-position, or a β-diketone residue connected at the α-position. Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine, and examples of the alkoxyl group having 1 to 6 carbon atoms which may have a substituent include a methoxy group, an ethoxy group and an isopropoxy group. Group, 2-chloroethoxy group, 2-methoxyethoxy group or the like has 1 carbon atom which may have a substituent.
Examples of the alkylthio groups of Nos. 6 to 6 include a methylthio group, an ethylthio group, a 2-hydroxyethylthio group, a 2-cyanoethylthio group, a 2-hydroxypropylthio group, a 2-acetoxyethylthio group, and a 2-methanesulfonylethylthio group. Examples of the alkylsulfinyl group having 1 to 6 carbon atoms which may have a substituent include a methylsulfinyl group, an ethylsulfinyl group, a 2-hydroxyethylsulfinyl group, and a 2-acetylaminoethylthio group. −
A cyanoethylsulfinyl group, a 2-hydroxypropylsulfinyl group, a 2-acetoxyethylsulfinyl group,
Examples of a 2-methanesulfonylethylsulfinyl group, a 2-acetylaminoethylsulfinyl group, and an alkylsulfonyl group having 1 to 6 carbon atoms which may have a substituent include a methylsulfonyl group, an ethylsulfonyl group,
2-hydroxyethylsulfonyl group, 2-cyanoethylsulfonyl group, 2-hydroxypropylsulfonyl group, 2
-Acetoxyethylsulfonyl group, 2-methanesulfonylethylsulfonyl group, 2-acetylaminoethylsulfonyl group and the like. Examples of the phenoxy group which may have a substituent include a phenoxy group,
Examples of the phenylthio group which may have a substituent such as a methylphenoxy group and a 4-hydroxyphenoxy group include a phenylthio group, a 4-methylphenylthio group,
Examples of a phenylsulfinyl group in which a -hydroxyphenylthio group or the like may have a substituent include a phenylsulfinyl group, a 4-methylphenylsulfinyl group, a 4-hydroxyphenylsulfinyl group, and the like. Examples of the phenylsulfonyl group which may be mentioned include a phenylsulfonyl group, a 4-methylphenylsulfonyl group, and a 4-hydroxyphenylsulfonyl group.

Next, an optionally substituted carbon number 2
Examples of the dialkylamino group of to 12 include a dimethylamino group, a diethylamino group, a diisopropylamino group,
Examples of the dicyclohexylamino group and the like, an N-alkoxyalkylamino group having 2 to 12 carbon atoms which may have a substituent include an N-methoxymethylamino group and the like.
Examples of the 5- or 6-membered nitrogen-containing heterocyclic residue which may have a substituent connected by a nitrogen atom include pyrrolidine, piperidine, morpholine, pyrazole, 3-methylpyrazole, 1,2,2 Examples of the 5- or 6-membered heterocyclic sulfide group in which the residue of the nitrogen-containing heterocyclic compound such as 4-triazole or 4,5-dihydropyrazole may have a substituent include 2- Pyridinylthio group, 2-pyrimidinylthio group, (4-methylpyrimidin-2-yl) thio group, 2-thiophenylthio group, (1,
(3-thiazol-2-yl) thio group, (2-methylfuran-3-yl) thio group, (1-methylimidazole-2)
—Yl) thio group and the like. Further, examples of malonic ester residues connected at the α-position include dimethylmalonic acid residues and diethylmalonic acid residues, and examples of β-ketoester residues connected at the α-position include acetoacetic acid. Examples of a β-diketone residue in which a methyl residue, an ethyl acetoacetate residue and the like are connected at the α-position include an acetylacetone residue and a 1,3-cyclohexanedione residue. This Q is particularly preferably a hydroxyl group.

X is a halogen atom, a nitro group, a cyano group,
R ⁸ , OR ⁸ , SR ⁸ , SO ₂ R ⁸ or NR ⁸ R ⁹ are shown. R ⁸
And R ⁹ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
Alkenyl group, alkynyl group having 2 to 6 carbon atoms, phenyl group or benzyl group. Here, examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include:
Methyl group, ethyl group, isopropyl group, cyclopropyl group, cyclohexyl group, trichloromethyl group, difluoromethyl group, trifluoromethyl group, methoxymethyl group, etc. Examples of the alkenyl group include an ethenyl group, an allyl group, a 1-propenyl group, and a 1-ethoxyethenyl group. Examples of the phenyl group in which a group, a 1-propynyl group, a 2-propynyl group and the like may have a substituent include a phenyl group and a 4-methylphenyl group which may have a substituent Examples of the benzyl group include a benzyl group and an α-methylbenzyl group. NR
^{In 8} R ⁹ , R ⁸ and R ⁹ may be the same or different, and R ⁸ and R ⁹ may be bonded to each other to form a ring structure. Examples of this ring structure include:
Examples include a pyrrolidine ring, a piperidine ring, a morpholine ring and the like. X represents a chlorine atom, a bromine atom, a nitro group, a cyano group, and a carbon atom having 1 to 5 carbon atoms which may have a substituent.
6 alkyl groups, specifically, a methyl group, an ethyl group, a trifluoromethyl group, and a methoxymethyl group are preferred.

Y represents O, S, SO or SO ₂ , preferably S, SO or SO ₂ . n is 0, 1 or 2
Is preferably 2, and p is 1 or 2.
Among the benzothiophene derivatives represented by the general formula (I), in particular, the general formula (Ia)

[0018]

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Wherein R ^{1 to} R ⁷ , Q, X, Y, n and p
Is the same as above. Those having the structure represented by ()) are preferable. When Q is a hydroxyl group, the benzothiophene derivative represented by the general formula (I) can have a tautomer structure as shown below. And mixtures thereof.

[0020]

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When R ¹ or R ⁶ is a hydrogen atom, the benzothiophene derivative represented by the general formula (I) can have a tautomer structure as shown below. The benzothiophene derivative of the present invention includes all these compounds and mixtures thereof.

[0022]

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The benzothiophene derivative represented by the general formula (I) of the present invention is, for example, WO00 / 20408 except for the introduction of a substituent at the 2-position of benzothiophene shown below.
Can be obtained by the method described in Japanese Unexamined Patent Publication No. (1) The carboxylic acid compound (III) obtained by the method described in WO 00/20408 is reacted with an alcohol to obtain an ester compound (IV).

[0024]

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(ROH is a lower alcohol such as methanol or ethanol, and X and p are the same as described above.) In this reaction, a catalytic amount of a protic acid such as sulfuric acid or p-toluenesulfonic acid is used. Alcohol is methanol,
Ethanol is preferred and is used in equimolar or more. As a reaction solvent, an inert solvent such as benzene or toluene can be used or can be used without a solvent. In carrying out this reaction, stirring may be performed at a temperature between room temperature and the boiling point of the solvent until the reaction is completed while removing water produced by the reaction. (2) The ester compound (IV) obtained in the above (1) is reacted with a halogenating agent to obtain a halide (V).

[0026]

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(Z: halogen atom) In this reaction, a halogenating agent such as N-promosuccinimide (NBS) is used in an equimolar amount or more in an inert solvent such as carbon tetrachloride. Azobisisobutyronitrile (AIBN) or the like is used as a radical generator in a catalytic amount. When performing this reaction, stirring may be performed until the reaction is completed at the boiling point of the solvent. (3) The halide (V) obtained in the above (2) is dehydrohalogenated to obtain a benzothiophene compound (VI).

[0028]

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In this reaction, a base such as triethylamine is used in an equimolar amount or more in an inert solvent such as methylene chloride. In carrying out this reaction, stirring may be carried out from 0 ° C. to the boiling point of the solvent until the reaction is completed. (4) Benzothiophene compound (VI) obtained in (3) above
And a substituent is introduced into the 2-position of the benzothiophene ring in to obtain compound (VII).

[0030]

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(R ⁷ and Y are the same as described above.) In this reaction, a nucleophile such as a sodium salt of methanethiol is equimolar or more in a two-layer system of an inert solvent such as methylene chloride and water. Used. As a layer transfer catalyst, a catalytic amount of tetrabutylammonium bromide (TBAB) or the like is used. In carrying out this reaction, stirring may be performed from room temperature to the boiling point of the solvent until the reaction is completed. (5) The carboxylic acid compound (VIII) is obtained by hydrolysis of the compound (VII) obtained in the above (4).

[0032]

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In this reaction, a mixed solvent of water and a protic solvent such as methanol and ethanol, and if necessary, an inert solvent such as methylene chloride are further added.
Bases such as sodium hydroxide and lithium hydroxide are used in equimolar or more. In carrying out this reaction, stirring may be carried out from 0 ° C. to the boiling point of the solvent until the reaction is completed. From the carboxylic acid compound (VIII) obtained above, for example, WO00
/ 20408 can obtain the benzothiophene derivative represented by the general formula (I) of the present invention. The herbicidal composition of the present invention contains the benzothiophene derivative represented by the general formula (1) obtained as described above as an active ingredient, and is particularly suitable for paddy rice. A benzothiophene derivative is mixed with a liquid carrier such as a solvent or a solid carrier such as a mineral fine powder,
It can be formulated and used in the form of wettable powders, emulsions, powders or granules. Further, in formulating the herbicidal composition, a surfactant may be added to impart emulsifiability, dispersibility, spreadability, and the like to the composition.

When the herbicidal composition of the present invention is used in the form of a wettable powder, the benzothiophene derivative is usually used in an amount of from 5 to 55%.
%, A composition containing 40 to 93% by weight of a solid carrier and 2 to 5% by weight of a surfactant may be used for weeding. When the herbicidal composition of the present invention is used in the form of an emulsion, usually 10 to 50% by weight of a benzothiophene derivative, 35 to 85% by weight of a solvent and 5 to 15% by weight of a surfactant are blended. A prepared composition may be prepared and used for weeding. When the herbicidal composition of the present invention is used in the form of a powder, 1 to 15% by weight of a benzothiophene derivative and 80 to 90% by weight of a solid carrier are usually used.
A composition in which 97% by weight and a surfactant are blended at a ratio of 2 to 5% by weight may be prepared and used. Furthermore, when the herbicidal composition of the present invention is used in the form of granules, usually, the benzothiophene derivative is 1 to 15% by weight, the solid carrier is 80 to 97% by weight, and the surfactant is 2 to 5% by weight. %
What is necessary is just to use the thing mix | blended the composition mix | blended by the ratio of the above for the weeding.

Examples of the solid carrier used herein include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as gypsum, talc, pyroferrite, clay, kaolin, bentonite, acid clay, Suitable examples include fine powders of mineral substances such as white carbon, quartz powder and silica stone powder. Further, as the solvent, for example, benzene, aromatic hydrocarbons such as toluene or xylene, o-chlorotoluene, chlorinated hydrocarbons such as trichloroethane or trichloroethylene, cycloxanol, amyl alcohol, alcohols such as ethylene glycol, isophorone, Organic solvents such as ketones such as cyclohexanone, cyclohexenyl-cyclohexanone, ethers such as butyl cellosolve, diethyl ether and methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate and methyl phthalate, amides such as dimethylformamide, and mixtures thereof are preferred. It is mentioned as a thing.

Further, as the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants such as amino acids and betaine can be used. The herbicidal composition of the present invention may contain, as an active ingredient, a component having another herbicidal activity, if necessary, together with the benzothiophene derivative represented by the general formula (I). Such other herbicidal active ingredients include, for example, diphenyl ether type, triazine type, urea type, carbamate type, thiocarbamate type, acid anilide type, pyrazole type, phosphoric acid type, sulfonylurea type, oxadiazon type and the like. Herbicidal active ingredients can be appropriately selected and used in combination. Further, the herbicidal composition of the present invention may contain an insecticide, a bactericide, a plant growth regulator, a fertilizer, and the like, if necessary.

The herbicidal composition of the present invention is applied to a weed or its growing area before or after the germination of the weed. The application means varies depending on the type of the cultivated plant and the use environment, but for example, methods such as spraying, spraying, watering, and water injection can be adopted. The dosage of the compound of the present invention is determined in consideration of various conditions such as the form of the preparation, the method of spraying, the type and amount of weeds, and the growth status. Normal 0.025-5kg
/ Ha, preferably 0.05 to 2 kg / ha, and those skilled in the art can easily determine the effective amount for obtaining the necessary herbicidal effect. Examples of the cultivated plants include rice, wheat, barley, corn, oat,
Grass plants such as sorghum, soybeans, cotton, beets,
In addition to broadleaf crops such as sunflower and rapeseed, fruit trees, vegetables such as fruit and root vegetables, leafy vegetables, and lawns are included.

The weeds to be controlled by the herbicidal composition of the present invention include paddy weeds (Paddy weeds).
s) Spiderfish (Alisma canalicu)
latum), Omodaka (Sagittaria tr)
ifolia), Urikawa (Sagittaria p.
arigatidae (Alismatac) such as Ygmaea)
eae) Weed, Cyperus dif (Cyperus dif)
formis), Oyster frog (Cyperus se)
rotinus), fireflies (Sirpusjunc)
oides), Krogwai (Eleocharisk)
uroguwai) and Cyperaceae (Cyper)
aceae) Weed, Azena (Lindernia py)
xidaria) and other Scrophulariaceae (Scroph)
ulariaceae, weeds, monocho (Monocho)
Ria vaginalis and other waterworms (P
ontenderiaceae weed, Hirumushiro (P
Potamogetonaceae weeds, such as otamogeton distinctus, Lythraceae weeds, such as Rotala indica, and Echinochloa crane grasses such as Echinochloa crane.

The field weeds include dogwood (S)
Solanaceae weeds, such as olanum nigrum and Datura stramonium, and Abutil
on theophrastis, Malus family such as American deer (Sida spinosa)
vaseae) Weed, Malva morning glory (Ipomoea)
Convolvulaceae (Convol) such as purpurea
vulaceae), weed, Amaranthus (Amaranth)
alive (Amarant) such as C. us lividus
haceae) Weeds, Xanthium s
trumium), ragweed (Ambrosia)
artemisfolia)
insiga ciliata), thistle (Cirsium arvense), and swordfish (S
enecio Vulgaris), Himejiyon (Er)
Asteraceae (Compo) such as igeron annus
sitae) Weeds, Dogs (Rorippa in)
dica), Sawfish (Sinapis arve)
nsis), Nazuna (Capsella bursa-
pastoris) (Brassic)
aceae) Weed, Polygonum b
ulumei), buckwheat (Polygonum c)
onvolvulus, etc. (polygon)
aceae) weed, purslane (Portulaca)
oleracea, etc. (Portul)
aceacee) weed, Shiroza (Chenopodiu)
malbum), core kaza (Chenopodium)
ficiolium), Kochi s
coparia etc. (Chenopodi)
aceae) Weed, Chickweed (Stellaria me)
dia) etc. (Caryophyllaceae)
ae) Weeds, P. persica (Veronica p.
erica) and other Scrophulariaceae (Scrophu)
lariacae) weeds, communis (Commeli)
na communis) and communis (Comm)
elinaceae) Weeds, Photohenosa (Lamium)
(Euphorbiaceae) weeds, such as amplexicaule, Euphorbia supina, and Euphorbia maculata, weeds, Gallium spur
Rubiaceae (Rubi) such as Gallium aparine and Rubia akane
aceae) Weeds, violets (Viola arvens)
is) and other Violaceae (Vilaceae) weeds, Sesbania exaltat
a), lobster (Cassia obtusifol)
ia) and broad-leaved weeds such as Leguminosae weeds.
s), wild sorghum (Sorghumbicolo)
r), Panicum dichoto (Panicum dichoto)
miflorum), Johnsongrass (Sorghu)
m haepense, dog millet (Echinoch)
loa crus-galli), crabgrass (Digi)
taria adscendes), oats (Av
ena fatua, Hawkgrass (Eleusine)
indica), Enokorogosa (Setaria vi)
ridis) or Sparrow Note (Alopec)
urus aequalis) and other grass weeds (Gr.)
amiaceous weeds, hamasuge (Cy)
perus rotundus, Cyperus es
culentus) and other Cyperaceae weeds (Cyp)
erase weeds).

[0040]

Next, the present invention will be described in more detail with reference to production examples and herbicide examples, but the present invention is not limited to these examples. Example 1 [1] Synthesis of 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophen-1,1-dioxide (1) 4-chloro-5-ethoxycarbonyl-2,3-
Synthesis of dihydrobenzothiophene-1,1-dioxide 0.1 g of p-toluenesulfonic acid in a solution of 3.0 g of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide in 15 ml of ethanol
Was added to the reflux tube, and molecular sieve 4A was filled therein, and the mixture was heated under reflux for 12 hours. After the reaction solution was cooled to room temperature, water was added, and the precipitated solid was filtered and dried to obtain 3.2 g of the desired ester compound.

(2) 4-chloro-5-ethoxycarbonyl-3-bromo-2,3-dihydrobenzothiophene
Synthesis of 1,1-dioxide AIBN 0.1 g was added to a suspension of 1.0 g of the ester compound and 0.71 g of NBS in 10 ml of carbon tetrachloride, and the mixture was heated under reflux for 16 hours. Water was added to the reaction mixture, extracted with ethyl acetate, washed with an aqueous sodium carbonate solution and saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.3 g of the desired bromo compound. (3) Synthesis of 4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide To a solution of 2.1 g of the bromo compound in 15 ml of methylene chloride was added dropwise a solution of 1 ml of triethylamine in 5 ml of methylene chloride at room temperature. After stirring at room temperature for 1.5 hours, 5% hydrochloric acid was added, extracted with methylene chloride, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.7 g of the desired benzothiophene compound.

(4) Synthesis of 4-chloro-5-ethoxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide A solution of 4.0 g of a benzothiophene compound and TBAB in 30 ml of methylene chloride was added at room temperature. Then, 10 ml of a 15% aqueous solution of methanethiol sodium salt was added, and the mixture was stirred for 4 hours. Water was added to the reaction mixture, extracted with methylene chloride, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography to obtain 2.3 g of the target sulfide compound. (5) Synthesis of 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide 2.5 g of a sulfide compound and 12.4 m of methylene chloride.
l, 12.4 ml of methanol and 6.29 ml of water were added at room temperature to 0.39 g of lithium hydroxide monohydrate,
Stir for 4 hours. To the reaction mixture was added 5% hydrochloric acid, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.2 g of the desired carboxylic acid compound. The obtained carboxylic acid compound was subjected to ¹ H-NMR [pp
m; acetone-d ⁶ (TMS standard)]
3 (3H, s), 3.17 (1H, dd), 3.87 (1H, dd), 4.79 (1H, dd), 7.
Absorption was observed at 83 (1H, d) and 8.05 (1H, d). From these results, it was confirmed that the obtained compound was 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide.

[2] 4-chloro-2-methylthio-5-
Synthesis of (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 1) 4-chloro-5-oxycarbonyl-2-methylthio-
To a suspension of 1.8 g of 2,3-dihydrobenzothiophene-1,1-dioxide in 10 ml of 1,2-dichlorotan was added 0.55 ml of thionyl chloride and 0.05 ml of N, N-dimethylformamide (DMF). Heated to reflux for an hour. The solvent of the reaction mixture was distilled off under reduced pressure, a solution of 0.85 g of 1,3-cyclohexanedione in 10 ml of acetonitrile was added, and a solution of 2.2 ml of triethylamine in 5 ml of acetonitrile was added dropwise at room temperature. The reaction mixture is allowed to
After stirring for 0.1 hour, 0.1 ml of acetone cyanohydrin was added, and the mixture was further stirred at room temperature for 7 hours. A 10% aqueous sodium hydroxide solution was added to the reaction mixture, which was washed with methylene chloride.
After adding concentrated hydrochloric acid to the aqueous layer to obtain an acidic solution, the mixture was extracted with methylene chloride. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 1.6 g of the target compound. The above [2]
Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the product obtained in 1. According to these measurement results, the product obtained here was 4-chloro-2-methylthio-5-
(1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 1).

Example 2 [1] 4-Chloro-2-ethylthio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-
Synthesis of dihydrobenzothiophene 1,1-dioxide (compound No. 2) 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1 used in [2] of Example 1 4-chloro-5 instead of -dioxide
A target compound was obtained in the same manner as in [2] of Example 1, except that -oxycarbonyl-2-ethylthio-2,3-dihydrobenzothiophene-1,1-dioxide was used. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 3 [1] 4-chloro-2- (2-propyl) thio-5-
Synthesis of (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 3) 4-chloro- used in [2] of Example 1 Instead of 5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide, 4-chloro-5
-Oxycarbonyl-2- (2-propyl) thio-2,
Except using 3-dihydrobenzothiophene-1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 4 [1] 4-Chloro-2- (1-propyl) thio-5-
Synthesis of (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 4) 4-chloro- used in [2] of Example 1 Instead of 5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide, 4-chloro-5
-Oxycarbonyl-2- (1-propyl) thio-2,
Except using 3-dihydrobenzothiophene-1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 5 [1] 4-Chloro-2- (2-methoxyethyl) thio-
5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-
Synthesis of Dioxide (Compound No. 5) In place of 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophen-1,1-dioxide used in [2] of Example 1, 4 -Chloro-5
Except that -oxycarbonyl-2- (2-methoxyethyl) thio-2,3-dihydrobenzothiophene-1,1-dioxide was used, the target compound was obtained in the same manner as in [2] of Example 1. . Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 6 [1] 4-chloro-2- (2,2-diethoxyethyl)
Thio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene
Synthesis of 1,1-dioxide (Compound No. 6) The 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide used in [2] of Example 1 was synthesized. Alternatively, 4-chloro-5
-Oxycarbonyl-2- (2,2-diethoxyethyl) thio-2,3-dihydrobenzothiophene-1,1
A target compound was obtained in the same manner as in [2] of Example 1, except that -dioxide was used. The obtained compound ¹ H-
Table 1 shows the results of NMR and infrared spectrum analysis, the chemical structural formula, and the measurement results of the melting point.

Example 7 [1] 4-Chloro-2- (2-oxoethyl) thio-5
Synthesis of-(1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 7) 4-chloro used in [2] of Example 1 Instead of -5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide, 4-chloro-5
-Oxycarbonyl-2- (2-oxoethyl) thio-
Except using 2,3-dihydrobenzothiophene-1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 8 [1] 4-chloro-2- (2-methoxyiminoethyl)
Thio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene
Synthesis of 1,1-dioxide (Compound No. 8) The 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide used in [2] of Example 1 was synthesized. Alternatively, 4-chloro-5
-Oxycarbonyl-2- (2-methoxyiminoethyl) thio-2,3-dihydrobenzothiophene-1,1
A target compound was obtained in the same manner as in [2] of Example 1, except that -dioxide was used. The obtained compound ¹ H-
Table 1 shows the results of NMR and infrared spectrum analysis, the chemical structural formula, and the measurement results of the melting point.

Example 9 [1] 4-Chloro-2- (2-hydroxyiminoethyl) thio-5- (1,3-dioxocyclohex-2-ene
Yl) Synthesis of carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (compound No. 9) 4-chloro-5-oxycarbonyl-2-methylthio-2,3 used in [2] of Example 1 -Instead of dihydrobenzothiophene-1,1-dioxide, 4-chloro-5
-Oxycarbonyl-2- (2-hydroxyiminoethyl) thio-2,3-dihydrobenzothiophene-1,1
A target compound was obtained in the same manner as in [2] of Example 1, except that -dioxide was used. The obtained compound ¹ H-
Table 1 shows the results of NMR and infrared spectrum analysis, the chemical structural formula, and the measurement results of the melting point.

Example 10 [1] 4-Methyl-2-methylthio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-
Synthesis of dihydrobenzothiophene 1,1-dioxide (compound No. 10) 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1 used in [2] of Example 1 4-methyl-5 instead of -dioxide
A target compound was obtained in the same manner as in [2] of Example 1, except that -oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide was used. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 11 [1] 2-methylthio-4-trifluoromethyl-5-
Synthesis of (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 11) 4-chloro- used in [2] of Example 1 Instead of 5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide, 5-oxycarbonyl-2-methylthio-4-trifluoromethyl-
Except using 2,3-dihydrobenzothiophene-1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 12 [1] 4-methoxy-2-methylthio-5- (1,3-
Dioxocyclohex-2-yl) carbonyl-2,3
Synthesis of -dihydrobenzothiophene 1,1-dioxide (Compound No. 12) 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1, used in [2] of Example 1, Instead of 1-dioxide, 4-methoxy-
Except that 5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene-1,1-dioxide was used, the target compound was obtained in the same manner as in [2] of Example 1. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 13 [1] 4-Chloro-2-methoxy-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. Synthesis of .13) In place of 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophen-1,1-dioxide used in [2] of Example 1, 4-chloro-2
-Methoxy-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide,
The target compound was obtained in the same manner as in [2] of Example 1. The ¹ H-NMR and infrared spectrum analysis results, chemical structural formula and melting point measurement result of the obtained target compound are shown in the first.
Shown in the table. Example 14 [1] 4-chloro-2-methoxy-5- (4,4-dimethyl-1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-
Synthesis of Dioxide (Compound No. 14) Example 1 was repeated except that 4,4-dimethyl-1,3-cyclohexanedione was used in place of 1,3-cyclohexanedione used in [2] of Example 1. The target compound was obtained in the same manner as in [2]. ¹ H-N of the obtained compound
Table 1 shows the results of the MR and infrared spectrum analysis, the chemical structural formula, and the measurement results of the melting point.

Example 15 [1] 4-chloro-2-methanesulfonyl-5- (1,
3-dioxocyclohex-2-yl) carbonyl-
Synthesis of 2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 15) 4-Chloro-2-methylthio-5- (1,3-dioxocyclohexa) obtained in [2] of Example 1 -2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
0.6 ml of a 30% aqueous hydrogen peroxide solution was added to a solution of 1.0 g of 1-dioxide in 5 ml of acetic acid, and the mixture was heated and stirred at 60 ° C. for 2 hours. Water was added to the reaction mixture, and the precipitated solid was collected by filtration.
After drying, 1.0 g of the target compound was obtained. ¹ H-NMR and infrared spectrum analysis results of the obtained target compound,
Table 1 shows the measurement results of the chemical structural formula and the melting point. Example 16 [1] 4-Chloro-2- (1-propane) sulfonyl-
5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-
Synthesis of Dioxide (Compound No. 16) 4-Chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 15
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2- (1-propyl) thio-5- (1,3-dioxocyclohexa-2
-Yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide except that the target compound was obtained in the same manner as in [1] of Example 15. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 17 [1] 4-Chloro-2-methylthio-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide Synthesis of (Compound No. 17) 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) obtained in [2] of Example 1
Carbonyl-2,3-dihydrobenzothiophene 1,
1.0 g of 1-dioxide, 5 m of 1,2-dichloroethane
1 solution contains 0.36 g of oxalyl chloride and 0.0
5 ml was added, and the mixture was heated and stirred at 60 ° C. for 1 hour. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography to obtain 1.0 g of the desired compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 18 [1] 4-chloro-2-methanesulfonyl-5- (3-
Chloro-1-oxo-2-cyclohexen-2-yl)
Carbonyl-2,3-dihydrobenzothiophene1,1
Synthesis of -dioxide (Compound No. 18) 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 17
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-2-methanesulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene instead of 1-dioxide
Except that 1,1-dioxide was used, [1] of Example 17 was used.
In the same manner as in the above, the target compound was obtained. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 19 [1] 4-Chloro-2-ethylthio-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide Synthesis of (Compound No. 19) 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 17
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2-ethylthio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1
A target compound was obtained in the same manner as in [1] of Example 17 except that -dioxide was used. ¹ H of obtained compound
Table 1 shows the results of NMR and infrared spectrum analysis, the chemical structural formula, and the melting point measurement results. Example 20 [1] 4-chloro-2-ethanesulfonyl-5- (3-
Chloro-1-oxo-2-cyclohexen-2-yl)
Carbonyl-2,3-dihydrobenzothiophene1,1
Synthesis of -dioxide (Compound No. 20) 4-Chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 17
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-2-ethanesulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene instead of 1-dioxide
Except that 1,1-dioxide was used, [1] of Example 17 was used.
In the same manner as in the above, the target compound was obtained. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 21 [1] 4-Chloro-2- (2-propyl) thio-5-
(3-chloro-1-oxo-2-cyclohexene-2-
Il) Synthesis of carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 21) 4-Chloro-2-methylthio-5- (1,3-dioxide) used in [1] of Example 17 Oxocyclohex-2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2- (2-propyl) thio-5- (1,3-dioxocyclohexa-2
-Yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide, except that the target compound was obtained in the same manner as in Example 17, [1]. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 22 [1] 4-chloro-2- (2-propane) sulfonyl-
5- (3-chloro-1-oxo-2-cyclohexene-
Synthesis of 2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (compound No. 22) 4-chloro-2-methylthio-5- (1,3) used in [1] of Example 17 -Dioxocyclohex-2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-2- (2-propane) sulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide in place of 1-dioxide Example 1 except for using
The target compound was obtained in the same manner as in 7 [1]. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 23 [1] 4-Chloro-2- (1-propyl) thio-5-
(3-chloro-1-oxo-2-cyclohexene-2-
Il) Synthesis of carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 23) 4-Chloro-2-methylthio-5- (1,3-dioxide used in [1] of Example 17 Oxocyclohex-2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2- (2-propyl) thio-5- (1,3-dioxocyclohexa-2
-Yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide, except that the target compound was obtained in the same manner as in Example 17, [1]. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 24 [1] 4-Chloro-2- (1-propane) sulfonyl-
5- (3-chloro-1-oxo-2-cyclohexene-
Synthesis of 2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 24) 4-chloro-2-methylthio-5- (1,3) used in [1] of Example 17 -Dioxocyclohex-2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-2- (1-propane) sulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide in place of 1-dioxide Example 1 except for using
The target compound was obtained in the same manner as in 7 [1]. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 25 [1] 4-Chloro-2- (2-methoxyethyl) thio-
5- (3-chloro-1-oxo-2-cyclohexene-
Synthesis of 2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (compound No. 25) 4-chloro-2-methylthio-5- (1,3) used in [1] of Example 17 -Dioxocyclohex-2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2- (2-methoxyethyl) thio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1- Example 1 except that a dioxide was used.
The target compound was obtained in the same manner as in 7 [1]. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 26 [1] 4-Chloro-2- (2-methoxyethane) sulfonyl-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene1, Synthesis of 1-dioxide (Compound No. 26) 4-Chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 17
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2- (2-methoxyethane) sulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1- Except using a dioxide, it carried out similarly to [1] of Example 17, and obtained the target compound. The ¹ H-NMR and infrared spectrum analysis results, chemical structural formula and melting point measurement result of the obtained target compound are shown in the first.
Shown in the table.

Example 27 [1] 4-chloro-2- (methoxycarbonylmethyl)
Synthesis of thio-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 27) [1] of Example 17 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-2- (methoxycarbonylmethyl) thio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide in place of 1-dioxide Except for using, the target compound was obtained in the same manner as in Example 17, [1]. The ¹ H-NMR and infrared spectrum analysis results, chemical structural formula and melting point measurement result of the obtained target compound are shown in the first.
Shown in the table. Example 28 [1] 4-chloro-2-methanesulfinyl-5- (3
-Chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene
Synthesis of 1,1-dioxide (Compound No. 28) 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 17
Carbonyl-2,3-dihydrobenzothiophene 1,
Instead of 1-dioxide, 4-chloro-2-methanesulfinyl-5- (1,3-dioxocyclohexa-2-
Yl) The target compound was obtained in the same manner as in [1] of Example 17, except that carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide was used. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 29 [1] 4-chloro-2-methylthio-5- [3- (4-
Synthesis of methylphenyl) thio-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 29) Obtained in Example 17, [1]. 0.50 g of 4-chloro-2-methylthio-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide and 4-methylbenzenethiol . To a solution of 16 g of methylene chloride in 5 ml was added dropwise 0.20 ml of triethylamine at room temperature. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography to obtain 0.50 g of the desired compound. ¹ H-N of the obtained compound
Table 1 shows the results of the MR and infrared spectrum analysis, the chemical structural formula, and the measurement results of the melting point. Example 30 [1] 4-Chloro-2-methylthio-5- (3-ethylthio-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-
Synthesis of Dioxide (Compound No. 30) Example 29 was repeated except that ethanethiol was used instead of 4-methylbenzenethiol used in [1] of Example 29.
[1] was obtained in the same manner as in [1]. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 31 [1] 4-chloro-2-methylthio-5- [3- (2-
Hydroxyethyl) thio-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 31)
The target compound was obtained in the same manner as in [1] of Example 29 except that 2-hydroxyethanethiol was used instead of 4-methylbenzenethiol used in [1] of Example 29. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 32 [1] 4-chloro-2-methylthio-5- [3- (2-
Synthesis of (cyanoethyl) thio-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (compound No. 32) 4- used in [1] of Example 29 Other than using 2-cyanoethanethiol instead of methylbenzenethiol,
The target compound was obtained in the same manner as in [29] of Example 29.
Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 33 [1] 4-chloro-2-methylthio-5- [3- (2-
(Hydroxy-1-propyl) thio-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (compound N
o. Synthesis of 33) The same procedures as in [1] of Example 29 were carried out, except that 2-hydroxy-1-propanethiol was used instead of 4-methylbenzenethiol used in [1] of Example 29. The compound was obtained. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 34 [1] 4-chloro-2-methylthio-5- [3- (2-
Acetoxyethyl) thio-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 34)
The target compound was obtained in the same manner as in [1] of Example 29 except that 2-acetoxyethanethiol was used instead of 4-methylbenzenethiol used in [1] of Example 29. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 35 [1] 4-chloro-2-methylthio-5- [3- (1-
Methyl imidazol-2-yl) thio-1-oxo-2
Synthesis of -cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 35) In place of 4-methylbenzenethiol used in [1] of Example 29, 2- Except that mercapto-1-methylimidazole was used, the target compound was obtained in the same manner as in [1] of Example 29. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 36 [1] 4-Chloro-2- (2-methoxyethane) sulfonyl-5- [3- (2-hydroxyethyl) thio-1-
Oxo-2-cyclohexen-2-yl] carbonyl-
Synthesis of 2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 36) 4-Chloro-2-methylthio-5- (3-chloro-1-oxo-2) used in [1] of Example 31 -Cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene Instead of 1,1-dioxide, 4-chloro-
2- (2-methoxyethane) sulfonyl-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1
A target compound was obtained in the same manner as in [31] of Example 31 except that -dioxide was used. ¹ H of obtained compound
Table 1 shows the results of NMR and infrared spectrum analysis, the chemical structural formula, and the melting point measurement results.

Example 37 [1] 4-Chloro-2-methylthio-5- (3-ethoxy-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-
Synthesis of Dioxide (Compound No. 37) 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) obtained in [2] of Example 1
Carbonyl-2,3-dihydrobenzothiophene 1,
To a solution of 1.0 g of 1-dioxide in 10 ml of methylene chloride was added 0.5 ml of diethylaminosulfur trifluoride under ice-cooling.
2 ml was added dropwise. After stirring at room temperature for 1 hour, the reaction mixture was washed with a saturated aqueous solution of sodium bicarbonate and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the obtained crude product was recrystallized from methanol to obtain 0.62 g of the desired compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 38 [1] 4-Chloro-2-methylthio-5- [3- (4,
5-dihydropyrazol-1-yl) -1-oxo-2
-Cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 38) 4-chloro-2-methylthio-5 obtained in [1] of Example 17 To a solution of 0.50 g of (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide in 5 ml of methylene chloride was added 0.4 ml of 4,5-dihydropyrazole at room temperature. 18 g were added. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography to obtain 0.39 g of the desired compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 39 [1] 4-Chloro-2-methylthio-5- [3- (pyrazol-1-yl) -1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzo Synthesis of thiophene 1,1-dioxide (Compound No. 39) The same as [1] of Example 38 except that pyrazole was used instead of 4,5-dihydropyrazole used in [1] of Example 38. Thus, the target compound was obtained. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 40 [1] 4-Chloro-2-methylthio-5- [3- (bis-methoxycarbonyl) methyl-1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1, 1-dioxide (Compound No.
Synthesis of 40) 0.15 g of 60% by weight sodium hydride 8 ml of benzene
0.49 g of dimethyl malonate was added to the suspension at room temperature.
After stirring at room temperature for 30 minutes, the 4-chloro-2-methylthio-5- (3-chloro-1) obtained in [1] of Example 17 was obtained.
-Oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (0.50 g) was added, and the mixture was heated under reflux for 2 hours. Ethyl acetate was added to the reaction mixture, washed with a 5% aqueous hydrochloric acid solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography to obtain 0.43 g of the desired compound. ¹ H of obtained compound
Table 1 shows the results of NMR and infrared spectrum analysis, the chemical structural formula, and the melting point measurement results.

Example 41 [1] 4-Bromo-2-methylthio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-
Synthesis of dihydrobenzothiophene 1,1-dioxide (compound No. 41) 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene 1,1- used in [2] of Example 1 4-bromo-5 instead of dioxide
Except that -oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene 1,1-dioxide was used, the target compound was obtained in the same manner as in [2] of Example 1. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 42 [1] 4-Iodo-2-methylthio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-
Synthesis of dihydrobenzothiophene 1,1-dioxide (compound No. 42) 4-chloro-5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene 1,1- used in [2] of Example 1 4-Iodo-5 instead of dioxide
Except that -oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene 1,1-dioxide was used, the target compound was obtained in the same manner as in [2] of Example 1. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 43 [1] 4-Chloro-7-methyl-2-methylthio-5-
Synthesis of (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 43) 4-chloro- used in [2] of Example 1 4-Chloro-7 instead of 5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene 1,1-dioxide
-Methyl-5-oxycarbonyl-2-methylthio-
Except using 2,3-dihydrobenzothiophene 1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 44 [1] 4-Chloro-7-methyl-2-ethylthio-5-
Synthesis of (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 44) 4-Chloro- used in [2] of Example 1 4-Chloro-7 instead of 5-oxycarbonyl-2-methylthio-2,3-dihydrobenzothiophene 1,1-dioxide
-Methyl-5-oxycarbonyl-2-ethylthio-
Except using 2,3-dihydrobenzothiophene 1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 45 [1] 4-Chloro-7-methyl-2- (2-methoxyethyl) thio-5- (1,3-dioxocyclohexa-2
Synthesis of -yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 45) 4-chloro-5-oxycarbonyl-2-methylthio-2, used in [2] of Example 1, 4-chloro-7 instead of 3-dihydrobenzothiophene 1,1-dioxide
-Methyl-5-oxycarbonyl-2- (2-methoxyethyl) thio-2,3-dihydrobenzothiophene
Except using 1,1-dioxide, it carried out similarly to [2] of Example 1 and obtained the target compound. Of the obtained target compound
Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula, and the melting point measurement results. Example 46 [1] 4-Chloro-7-methyl-2-methanesulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-
Synthesis of Dioxide (Compound No. 46) 4-Chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 15
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-7-methyl-2 instead of 1-dioxide
-Methylthio-5- (1,3-dioxocyclohexa-
Except that 2- (yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide was used, the target compound was obtained in the same manner as in [15] of Example 15. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 47 [1] 4-Chloro-7-methyl-2-ethanesulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1 −
Synthesis of Dioxide (Compound No. 47) 4-Chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 15
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-7-methyl-2 instead of 1-dioxide
-Ethylthio-5- (1,3-dioxocyclohexa-
Except that 2- (yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide was used, the target compound was obtained in the same manner as in [15] of Example 15. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 48 [1] 4-Chloro-7-methyl-2- (2-methoxyethane) sulfonyl-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1 , 1-Dioxide (Compound No. 48) Synthesis of 4-chloro-2-methylthio-5- (1,3-dioxocyclohex-2-yl) used in [1] of Example 15
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-7-methyl-2 instead of 1-dioxide
Example 15 except that [-(2-methoxyethyl) thio-5- (1,3-dioxocyclohex-2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide was used. In the same manner as in 1), the target compound was obtained. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 49 [1] 4-Chloro-7-methyl-2-methylthio-5-
(3-chloro-1-oxo-2-cyclohexene-2-
Yl) Synthesis of carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 49) 4-chloro-2-methylthio-5- (1,3-dioxide) used in [1] of Example 17 Oxocyclohex-2-yl)
Carbonyl-2,3-dihydrobenzothiophene 1,
4-chloro-7-methyl-2 instead of 1-dioxide
-Methylthio-5- (1,3-dioxocyclohexa-
Except that 2-yl) carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide was used, the target compound was obtained in the same manner as in [1] of Example 17. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 50 [1] 4-Chloro-7-methyl-2-methylthio-5-
[3- (2-hydroxyethyl) thio-1-oxo-2
Synthesis of -cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (Compound No. 50) 4-chloro-2-methylthio-5- ( 3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene Instead of 1,1-dioxide, 4-chloro-
7-methyl-2-methylthio-5- (3-chloro-1-
Oxo-2-cyclohexen-2-yl) carbonyl-
Except using 2,3-dihydrobenzothiophene 1,1-dioxide, it carried out similarly to [1] of Example 31 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

Example 51 [1] 4-Chloro-7-methyl-2-methylthio-5-
[3- (2-chloroacetoxyethyl) thio-1-oxo-2-cyclohexen-2-yl] carbonyl-2,
Synthesis of 3-dihydrobenzothiophene 1,1-dioxide (Compound No. 51) 4-chloro-2-methylthio-5- (3-chloro-1-oxo-2-cyclohexene used in [1] of Example 29 -2-yl) carbonyl-2,3-dihydrobenzothiophene Instead of 1,1-dioxide, 4-chloro-
7-methyl-2-methylthio-5- (3-chloro-1-
Oxo-2-cyclohexen-2-yl) carbonyl-
The target compound was obtained in the same manner as in [1] of Example 29, except that 2,3-dihydrobenzothiophene 1,1-dioxide was replaced with 2-chloroacetoxyethanethiol instead of 4-methylbenzenethiol. Was. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound. Example 52 [1] 4-Chloro-7-methyl-2-methylthio-5-
[3- (pyrazol-1-yl) -1-oxo-2-cyclohexen-2-yl] carbonyl-2,3-dihydrobenzothiophene 1,1-dioxide (compound N
o. Synthesis of 52) 4-chloro-2-methylthio-5- (3-chloro-1-oxo-2-cyclohexen-2-yl) carbonyl-2,3-dihydrobenzothiophene used in [1] of Example 39 4-chloro- in place of 1,1-dioxide
7-methyl-2-methylthio-5- (3-chloro-1-
Oxo-2-cyclohexen-2-yl) carbonyl-
Except using 2,3-dihydrobenzothiophene 1,1-dioxide, it carried out similarly to [1] of Example 31 and obtained the target compound. Table 1 shows the ¹ H-NMR and infrared spectrum analysis results, the chemical structural formula and the measurement results of the melting point of the obtained target compound.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

[Table 5]

[0075]

[Table 6]

[0076]

[Table 7]

[0077]

[Table 8]

[0078]

[Table 9]

[0079]

[Table 10]

[0080]

[Table 11]

Examples of Herbicides [1] Preparation of Herbicide Compositions 57 parts by weight of talc and 40 parts by weight of bentonite were used as carriers, and 3 parts by weight of sodium alkylbenzene sulfonate were used as a surfactant. Thus, a carrier for a wettable powder was obtained. Next, 10 parts by weight of the benzothiophene derivative obtained in the production example was added to 90 parts by weight of the carrier for wettable powder, and the mixture was uniformly ground and mixed to obtain a herbicidal composition. [2] Herbicidal test (1) Flooding test / post-treatment test for 3 days after transplanting Paddy field soil was filled in a 1/2000 arel wagnal pot, and seeds of Canine fireflies were sown on the surface layer. The leaf stage rice seedlings were transplanted. Next,
Assuming that the depth of water in this pot is 3 cm,
They were placed in a greenhouse whose temperature was controlled to ２５25 ° C. and grown under plant growth conditions. And after transplanting rice seedlings 3
On the day, the herbicidal composition prepared in the above [1] was treated by adding a predetermined amount. On the 30th day after the chemical treatment, the herbicidal effect and the phytotoxicity on the rice were observed. The results are shown in Table 2.

(2) Flooding test / 10-day post-transplantation test A paddy field soil was filled in a Wagner pot of 1/2000 ares, and seeds of Insect firefly were sown on the surface layer. -Stage rice seedlings were transplanted. Next,
Assuming that the depth of water in this pot is 3 cm,
Plants were grown by placing them in a greenhouse whose temperature was controlled to ２５25 ° C. On the 10th day after transplanting the rice seedlings, the above [1]
A predetermined amount of the herbicidal composition prepared in the above was added for treatment. On the 30th day after the treatment, the herbicidal effect and the phytotoxicity on the rice were observed. The results are shown in Table 2.

The herbicidal effects and phytotoxicity in the herbicidal tests (1) and (2) were determined according to the following criteria. (A) Herbicidal rate The above-ground fresh grass weight in the chemical treatment area and the above-ground fresh grass weight in the non-treated area were measured, and the herbicidal rate (%) = [1- (the above-ground fresh grass weight in the chemical-treated area) / (Weight of above-ground raw grass in untreated area)] × 1
The weed kill rate (%) was calculated by the formula of 00.

(B) Herbicidal effect The herbicidal effect was determined according to the following criteria. Herbicidal effect Herbicidal rate 0 Less than 5% (almost no effect) 1 5% or more to less than 20% 2 20% or more to less than 40% 3 40% or more to less than 70% 4 70% to less than 90% 5 90% or more ( Almost completely withered)

(C) Chemical damage Chemical damage was determined according to the following criteria. 5 almost complete death of 4 phytotoxicity degree 0 phytotoxicity phytotoxicity phytotoxicity 1 Phytotoxicity not observed is observed 3 phytotoxicity 2 phytotoxicity is observed slightly not substantially observed were conspicuously observed

Comparative Examples of Herbicides [1] In the preparation of herbicide examples [1] instead of the benzothiophene derivative of the present invention, a compound (A) having the following structure (described in WO 00/20408) Compound] and compound (B) [SB-500 (development number of DS Biotech)] were used in the same manner as in the herbicide examples. The results are shown in Table 3.

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[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

The benzothiophene derivative of the present invention, when used as an active ingredient of a herbicide, has an excellent effect that it has little phytotoxicity to cultivated crops such as paddy rice and can control a wide range of weeds at a low dose. Is obtained. The herbicidal composition of the present invention containing the benzothiophene derivative,
It is particularly suitable for paddy rice.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H011 AB02 BA01 BB08 BB09 BC07 BC20 DA15 DC03 DC05 DD01

Claims (9)

[Claims] 1. A compound of the general formula (I) (Wherein, R ^{1 to} R ⁶ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms, and two groups selected from R ^{1 to} R ⁶ ) Two substituents may be bonded to each other to form a bicyclo ring together with the cyclohexene ring, and R ⁷ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent. , May have a halogen atom, or a substituent,
C1-C6 alkoxyl group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, phenoxy group, phenylthio group, phenylsulfinyl group, phenylsulfonyl Group, dialkylamino group having 2 to 12 carbon atoms, N-alkoxyalkylamino group having 2 to 12 carbon atoms, 5- or 6-membered nitrogen-containing heterocyclic residue connected by a nitrogen atom, or 5- or 6-membered A heterocyclic sulfide group, or a malonic ester residue connected at the α-position, a β-ketoester residue connected at the α-position, or a β- connected at the α-position.
Shows a diketone residue. X represents a halogen atom, a nitro group, a cyano group, R ⁸ , OR ⁸ , SR ⁸ , SO ₂ R ⁸ or NR ⁸ R ⁹ . R ⁸ and R ⁹ are each a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, phenyl, A benzyl group or a benzyl group, and in NR ⁸ R ⁹ , R ⁸ and R ⁹ may be the same or different, and R ⁸ and R ⁹ are bonded to each other to form a ring structure. It may be. Y represents O, S, SO or SO ₂ , n represents 0, 1 or 2, and p represents 1 or 2. A benzothiophene derivative represented by the formula: 2. A compound of the general formula (Ia) (Wherein R ^{1 to} R ⁷ , Q, X, Y, n, and p are the same as described above). 3. The benzothiophene derivative according to claim 1, wherein n is 2. 4. The benzothiophene derivative according to claim 1, wherein R ^{1 to} R ⁶ are all hydrogen atoms. 5. The benzo according to claim 1, wherein X is a chlorine atom, a bromine atom, a nitro group, a cyano group or an optionally substituted alkyl group having 1 to 6 carbon atoms. Thiophene derivatives. 6. The method according to claim 1, wherein Y is S, SO or SO _2.
6. The benzothiophene derivative according to any one of items 1 to 5. 7. The benzothiophene derivative according to claim 1, wherein Q is OH. 8. A herbicidal composition comprising the benzothiophene derivative according to claim 1 as an active ingredient. 9. The herbicidal composition according to claim 8, which is used for paddy rice.