JPH0674273B2 - Imidazol sulfonamide derivative, process and herbicide - Google Patents

Description

The present invention relates to a novel imidazolesulfonamide derivative, a method for producing the compound, and a herbicide containing the compound as an active ingredient. It is indispensable to use herbicides to protect important crops such as rice, wheat, corn, soybean, cotton and beet from weed damage and increase the yield. Particularly in recent years, in arable land where these useful crops and weeds are mixed, a selective herbicide capable of selectively killing only the weeds without showing phytotoxicity to the crops even when the foliage of the crops and the weeds are simultaneously treated is desired. It is rare. Also, environmental pollution prevention, transportation,
From the viewpoint of economic cost reduction at the time of application, exploratory research on compounds that show high herbicidal effect with the lowest possible dose has been continued for many years. Although some of the compounds with such properties are currently used as selective herbicides, there is still a need for new compounds with these properties.

The present inventors have continued to study for many years in order to develop a herbicide having selectivity for important crops, and to produce a compound having higher herbicidal activity and selectivity, many compounds are We have examined the weeding characteristics. As a result, the above general formula (I) [In the formula, B, DR, Q, T and m have the same meanings as described above. ] The imidazole sulfonamide derivative represented by the formula (hereinafter referred to as the compound of the present invention) has a strong herbicidal activity against many weeds and is highly safe against important crops in both soil treatment and foliar treatment. The present invention has been completed by finding out that it has a property. On the other hand, the compound of the present invention exhibits a high herbicidal activity at a very low dose as compared with conventional herbicides, and is therefore also useful as a herbicide for orchards and non-arable land.

As a prior art having a structure similar to that of the compound of the present invention, for example, JP-A-58-162587 and JP-A-59-1480 disclose imidazolesulfonylureas, but the compound of the present invention has a heterocyclic ring in imidazole. The substituted compound is a novel compound which has never been known so far.

The compound of the present invention represented by the general formula (I) can be easily produced by selecting one of the following reaction formulas 1 to 6.

Reaction formula 1 [In the formula, B, D, E, G, Q, R, W ¹ and m have the same meanings as described above. That is, the imidazolesulfonyl (thio) isocyanate derivative (II) is dissolved in a sufficiently dried inert solvent such as dioxane or acetonitrile, and then added to the formula (III)
By adding the pyrimidine, triazine or triazole derivative represented by and stirring, generally, the reaction is rapidly carried out to obtain (I) 'which is a part of the compound of the present invention. When the reaction is difficult to proceed, a suitable base such as triethylamine, triethylenediamine, pyridine,
The reaction proceeds easily by adding a very small amount of sodium alkoxide, sodium hydride or the like.

Reaction formula 2 [In the formula, B, D, E, G, Q, R, W ¹ and m have the same meanings as described above.
R ²⁹ represents a lower alkyl group or a phenyl group. ] That is, the imidazole sulfonamide derivative (V)
Compound (IV) is obtained by reacting with a chloroformic acid (thio) ester or a carbonic acid (thio) ester in the presence of a base such as potassium carbonate in a solvent such as acetone, methyl ethyl ketone or acetonitrile. Then, by heating the compound (III) in a solvent such as toluene, a part of the compound of the present invention (I) 'can be obtained.

Reaction formula 3 [In the formula, B, D, E, G, Q, R, m, R ²² and R ²³ have the same meanings as described above. ] Reaction formula 4 [In the formula, Az, B, D, E, G, Q, R, W ¹ , m, R ²² and R ²³ have the same meanings as described above. ] Reaction formula 5 [In the formula, Az, B, D, E, G, Q, R, and m have the same meanings as described above. That is, in reaction formulas 3 to 5, JP-A-59-167570, JP-A-60-6654, JP-A-60-36467,
According to the method described in JP-A-61-60670, JP-A-61-60684 and JP-A-61-72783, the above imidazole sulfonamide derivative which is a part of the compound of the present invention can be synthesized. it can.

Reaction formula 6 (In the formula, B, D, E, G, Q, R, W, and m have the same meanings as described above, H
al represents a halogen atom. That is, by reacting 1H-imidazolesulfonylurea with Hal- (CHR) _m -Q in the presence of a suitable base, (I) 'which is a part of the compound of the present invention can be obtained. However, when m is 0, in many cases, it is desirable to have an electron-withdrawing group such as a nitro group, CF _{3 or} a halogen atom as a substituent of Q, and it is necessary that the reactivity of the Hal-group is high.

The starting material imidazole sulfonyl (thio) isocyanate (II) or imidazole sulfonyl group (thio) carbamate derivative (I
For V), the method described below is appropriately selected to synthesize the imidazole sulfonamide (V), and the method described in European Patent Application Publication No. 87,780 and JP-A-55-13266 is used. It can be synthesized with reference.

The intermediate imidazole sulfonamide used in the present invention is also a novel compound, and these compounds are represented by the following reaction formulas 7 to 11:
Method and JP-A-58-162587 and JP-A-59-1480.
It can be obtained by appropriately selecting the method described in Japanese Patent Publication.

Reaction formula 7 Reaction formula 8 Reaction formula 9 Reaction formula 10 Reaction formula 11 (A) NaNO ₂ · HCl or NaNO ₂ · HBr (b) SO ₂ · Cu salt (c) NH ₄ OH or ammonium carbonate (d) Cu salt (e) NaSH (f) NaOH · NH ₄ OH / NaOCl (g ) Oxidizing agent (h) NaSCH ₂ Ph (i) Cl ₂ / CH ₃ CO ₂ H ・ H ₂ O or NaOCl / HCl (j) 1) ClSO ₃ H 2) SOCl ₂ or PCl ₃ (k) 1) BuLi or _{LiN (i-Pr) 2 2} ) SO 2 3) N- Kurorukohaku acid imide _{(l) Q- (CHR) m} -Hal / base [in Scheme 7~11, B, D, Q, R, m is the Has the same meaning as, and Hal represents a halogen atom. The imidazole sulfonamide (V) is usually obtained by reacting a reactive imidazole sulfonyl chloride with aqueous ammonia or ammonium carbonate. To introduce a sulfonyl group into the imidazole ring, diazonium decomposition of the amino group in the presence of sulfur dioxide to obtain an imidazole sulfonyl chloride, a halogen atom or the like is introduced into the imidazole ring by a nucleophilic substitution reaction, and further oxidation may be carried out in some cases. To obtain an imidazole sulfonyl chloride, to form a carbanion of imidazole using a base to react with sulfur dioxide, and then to obtain an imidazole sulfonyl chloride by halogenation, to directly obtain an imidazole by an electrophilic substitution reaction using chlorosulfonic acid, etc. Examples thereof include a method of obtaining sulfonyl chloride.

That is, according to reaction formula 7, aminoimidazole is converted to diazonium salt with sodium nitrite in hydrochloric acid or hydrobromic acid, and sulfur dioxide is allowed to act in the presence of a catalyst usually used for decomposing diazonium such as copper salt. To give the corresponding imidazole sulfonyl chloride. The target imidazole sulfonamide (V) is obtained by reacting this with ammonium hydroxide water.

According to reaction formula 8, a sulfur atom is introduced into the imidazole ring by treating halogenated imidazole with sodium sulfide, benzyl mercaptan sodium salt, etc., and imidazole sulfonyl chloride is converted by oxidation with chlorine in a solvent such as acetic acid / water. Obtainable. Reaction formula 7
Similarly to the above, the desired imidazole sulfonamide (V) is obtained by reacting with aqueous ammonia. The target imidazolesulfonamide (V) can also be obtained by converting the mercaptoimidazole obtained in the middle to sulfenamide and oxidizing this. The halogenated imidazole as a starting material is prepared by diazo decomposition of aminoimidazole, reaction of hydroxyimidazole with phosphorus oxychloride or phosphorus oxybromide or anion using a strong base such as butyllithium or lithium diisopropylamide, and then halogenated. You can also get

According to Reaction Scheme 9, a strong base such as butyllithium or lithium diisopropylamide is used to generate an anion on the imidazole ring, and further sulfur dioxide and N-halogenosuccinimide are treated to form imidazole sulfonyl chloride and treated with aqueous ammonia. Thus, the desired imidazole sulfonamide (V) can be obtained.

According to reaction formula 10, imidazole sulfonyl chloride can be directly obtained with chlorosulfonic acid.

In addition to the above, according to Reaction Scheme 11, an imidazolesulfonamide having no substituent at the 1-position is treated with a suitable halogen derivative Hal- (CHR) _m Q [in the formula, Q, R, m, Hal has the same meaning as described above. ] By reacting
The desired imidazole sulfonamide (V) can be obtained. The reaction conforms to reaction formula 6. In the reactions of reaction formulas 9 to 11, an isomer mixture may be produced depending on the case, but it can be separated by recrystallization or column chromatography and used as an intermediate of the compound of the present invention. General literature on the chemistry of the imidazoles used as starting materials for the above reactions include: MR Grimmett, Amvant Heterocyclic Chemistry (Adv.Heterocycl.Che
m.) 12 p. 104 1970, RC Elderf
ield), Heterocyclic Compounds (Heterocy
clic Compounds) Volume V, p. 194, 1957, Joan Willie & Sons Incorporated, New York (Wiley, New York), K. Shawfield (Schofie)
ld), MR Grimmett and BRT Keene, Heteroaromatic Nitrogen Compounds Di Azole (Heteroaromatic Nitrogen)
Compounds The Azoles) Cambridge University Press 1976, MR Grimmett, Comprehensive Heterocyclic C
vol. 5 345, 1984, Pergamon Press (Perga)
mon Press).

For example, regarding the mercaptoimidazole derivative, as shown in reaction formula 12, RG Jones, EC
Kornfeld, KC McCrawlin (Mc
LaughIin) and RC Anderson (Anderson), JA
m.Chem.Soc., 71, 4000, 1949 can be synthesized according to the method described therein.

Reaction formula 12 [In the formula, Q, R, R ¹¹ and m have the same meanings as described above,
B and D each independently represent a hydrogen atom or a lower alkyl group. ] Reaction formula 13 [Wherein Q, R, R ¹¹ , W ¹ , m and Hal have the same meanings as described above, B is a hydrogen atom, a lower alkyl group or a lower alkylmercapto group, and D is an alkylcarbonyl group, a benzoyl group, A cyano group, an alkylsulfonyl group, a phenylsulfonyl group, COOR ¹⁴ , or CONR ¹⁵ R ¹⁶ , R ¹⁴ ,
R ¹⁵ and R ¹⁶ have the same meanings as described above. ] Reaction formula 14 [In the formula, Q, R, R ¹¹ and m have the same meanings as described above,
B is a hydrogen atom or a lower alkyl group, D is a hydrogen atom,
An alkylcarbonyl group, a benzoyl group, a cyano group, an alkylsulfonyl group, a phenylsulfonyl group, COOR ¹⁴ or CONR ¹⁵ R ¹⁶ and R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meanings as described above. Regarding aminoimidazole, as shown in Reaction Scheme 13, K. Gewald and G. Heinhold (Hein
hold), Monatsh. Chem., 107, 1413, 1976, East German patent 1
18,640 bulletin and A. Edenhofe
r) 4-aminoimidazole derivatives having various substituents can be obtained by synthesizing according to the method described in Helv. Chim. Acta., Vol. 58, p. 2192, 1975. Further, regarding 5-aminoimidazole, reaction formula 14
DH Robinson and G. Shaw, J. Chem. Soc., Perkin Trans. I, 1715 p. 1972.
It can be synthesized according to the method described in the year.

Generally, a person skilled in the art can obtain an intermediate of the compound of the present invention by examining the experimental conditions and the like based on the above description and the above-mentioned known techniques. Hereinafter, synthesis examples of the compound of the present invention and an intermediate imidazole sulfonamide will be specifically described as Examples and Reference Examples, but the present invention is not limited thereto.

Reference Example 1 Synthesis of 1- (2-pyridyl) imidazole-2-sulfonamide (1) Synthesis of 1- (2-pyridyl) imidazole-2-thiol 2-pyridylisothiocyanate 11.1 g of ethanol 100
ml acetaldehyde diethyl acetal
10.0 g was added, and the mixture was stirred with heating under reflux for 40 minutes. After the reaction, the solvent was distilled off under reduced pressure, and the precipitated crystals were collected by filtration to obtain 13.8 g of N
-2,2-Diethoxyethyl-N '-(2-pyridyl)-
Thiourea (melting point 132-133 ° C) was obtained. To the obtained crystals
120 ml of 10% dilute hydrochloric acid was added, and the mixture was stirred for 30 minutes while heating under reflux.
The reaction mixture was cooled and the pH was adjusted to 5 to 6 with 50% aqueous sodium hydroxide solution, whereby crystals were precipitated. The precipitated crystals were filtered, washed with water and dried to obtain 8.3 g of the desired product. Melting point 162-163 ° C. (2) Synthesis of 1- (2-pyridyl) imidazole-2-sulfonamide 1- (2-pyridyl) imidazole-2-thiol 5.1
A mixture of g, 5.2 g of anhydrous potassium carbonate, 3.7 g of benzyl chloride and 50 ml of acetonitrile was stirred at room temperature for 4 hours.
After the reaction, the solid was filtered off, the filtrate was concentrated under reduced pressure, and the precipitated crystals were collected by filtration to obtain 7.1 g of 2-benzylthio-1- (2-pyridyl) imidazole (melting point: 76 to 77 ° C). 7.1 g of the obtained crystals, 50 ml of methylene chloride, 50 ml of water and 22 g of concentrated hydrochloric acid.
While stirring vigorously, 80 g of 6% sodium hypochlorite solution was added dropwise to the above mixture at -10 to 0 ° C over 1 hour.
After dropping, after stirring for 30 minutes at the same temperature, the organic layer was separated,
The aqueous layer was extracted with methylene chloride. The organic layers were combined and washed with water, and then 10 ml of 28% ammonia water was added dropwise to the organic layer with vigorous stirring under ice cooling. After the dropping, the mixture was stirred at room temperature for 1.5 hours, and the reaction mixture was concentrated to dryness under reduced pressure. The obtained concentrated residue was extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure to obtain 3.0 g of a crude target product. The crystals precipitated from the obtained crude product were collected by filtration to obtain 0.8 g of the desired product. Melting point 187-1
88 ° C. Reference Example 2 Synthesis of 4-ethoxycarbonyl-1- (2-pyridyl) imidazole-5-sulfonamide (1) 5-amino-4-ethoxycarbonyl-1- (2
-Pyridyl) imidazole synthesis: α-aminocyanoacetic acid ethyl 8.5 g, ethyl orthoformate 1
0.8 g and 2-aminopyridine 6.2 g were added to acetonitrile 23
The mixture was heated to reflux in 0 ml for 1.5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the precipitated crystals were filtered and washed with benzene to obtain 11.0 g of the desired product. Melting point 129-131 ° C (2) 4-ethoxycarbonyl-1- (2-pyridyl)
Synthesis of imidazole-5-thiol 11.0 g of 5-amino-4-ethoxycarbonyl-1- (2-pyridyl) imidazole was dissolved in 60 ml of concentrated hydrochloric acid to give -5
Cooled to ° C. Next, 3.9 g of sodium nitrite was dissolved in 10 ml of water and added dropwise while keeping the temperature at -5 ° C or lower.
The mixture was stirred at the same temperature for 0.5 hours. Add this solution to cuprous chloride
Chloroform solution containing 1.0 g and 12 g of sulfur dioxide 150
It was added dropwise to the mixture at around 5 ° C. After stirring at room temperature for 1 hour, water 30
0 ml was added and the organic layer was separated. The aqueous layer was extracted with chloroform, the organic layers were combined, washed with water, dehydrated and evaporated to remove 5-chloro-4-ethoxycarbonyl-1- (2-
11.6 g of pyridyl) imidazole was obtained as an oil.

11.6 g of the obtained 5-chloroimidazole derivative was dissolved in 30 ml of dimethylformamide, and sodium hydrosulfide (70%
(Containing) 9.2 g was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into ice water, the insoluble matter was filtered off, and the filtrate was concentrated hydrochloric acid,
When weakly acidic, the precipitated crystals are filtered, washed with water, and dried,
10.6 g of the desired product was obtained. Melting point 84-87 ° C (3) 4-ethoxycarbonyl-1- (2-pyridyl)
Synthesis of imidazole-5-sulfonamide 4-ethoxycarbonyl-1- (2-pyridyl) imidazole-5-thiol 10.6 g, water 50 ml, chloroform 100
ml and concentrated hydrochloric acid 35.5 g with vigorous stirring,
128g of sodium hypochlorite solution (6% content) -10 to 0 ° C
Was added dropwise over 1 hour. After the dropping, the mixture was stirred at the same temperature for 0.5 hours, the organic layer was separated, and the aqueous layer was extracted with chloroform. The organic layers were combined and washed with water. Then, 10 ml of 28% aqueous ammonia was added dropwise to the organic layer under ice cooling, and the mixture was stirred at room temperature for 1.5 hours. The reaction mixture was concentrated to dryness under reduced pressure, and the residue was extracted with ethyl acetate. After evaporating the solvent, the precipitated crystals were collected by filtration to obtain 4.1 g of the desired product. Melting point: 138 to 139 ° C. A specific synthesis example of the compound of the present invention is shown below using the intermediate obtained in the above Reference Example, but the present invention is not limited thereto.

Example 1 N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl] -1- (2-pyridyl) imidazole-2
-Synthesis of sulfonamide 1- (2-pyridyl) imidazole-2-sulfonamide 0.8 g, methyl chloroformate 0.5 g, anhydrous potassium carbonate 0.75
g was heated to reflux in 15 ml of acetonitrile for 1 hour. After the reaction, the solvent was distilled off under reduced pressure, ice water was added, and the mixture was extracted with methylene chloride. The aqueous layer was made weakly acidic with diluted hydrochloric acid and concentrated under reduced pressure to precipitate crystals. The precipitated crystals are filtered off, washed with water,
When dried, 0.46 g of N- [1- (2-pyridyl) imidazole-2-sulfonyl] methylcarbamate was obtained.
Melting point 154-156 ° C. 0.46 g of the obtained methyl carbamate and 2-amino-
0.25 g of 4,6-dimethoxypyrimidine was heated to reflux for 1.5 hours while distilling toluene little by little in 30 ml of toluene.
After the reaction, the mixture was filtered while hot, and the crystals precipitated from the filtrate were separated by filtration to obtain 0.3 g of the desired product. Melting point 146-149 ° C However, the symbols in the table have the following meanings.

Me: methyl group, Et: ethyl group, Pr-n: normal propyl group, Pr-i: isopropyl group, and Gn have the following meanings. Group, Ga = G _{1 to} G ₃₅ , Gb = G _{1 to} G ₆ , Gc = G _{1 to} G ₃ Qn has the following meanings.

J1 to J5 have the following meanings.

The compounds synthesized according to the above Examples and the physical properties thereof are shown below.

In applying the compound of the present invention as a herbicide, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, diatomaceous earth or water, alcohol (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, Xylene etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate etc.), acid amides (dimethylformamide etc.), etc. By adding a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer and the like, it can be put into practical use in any dosage form such as a liquid, emulsion, wettable powder, granule and granule.

Next, formulation examples of a herbicide containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In the following formulation examples, "part" means part by weight.

Formulation Example 1 Wettable powder Compound of the present invention No4 ...... 20 parts Dikrite A ...... 76 parts (Kaolin clay: product name of Sikhlite Industry Co., Ltd.) Sorpol 5039 ...... 2 parts (Nonionic surfactant and anion Mixture with water-soluble surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) …… 2 parts (White carbon: Shionogi Seiyaku Co., Ltd. trade name) Use as a Japanese medicine.

Formulation Example 2 Wettable powder Compound No. 1 of the present invention ...... 40 parts Diquelite A …… 54 parts (Kaolin clay: product name of Sikelite Industry Co., Ltd.) Sorpol 5039 …… 2 parts (Nonionic surfactant and anion Mixture with water-soluble surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) …… 4 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) Use as a Japanese medicine.

Formulation Example 3 Emulsion compound No. 2 ...... 5 parts Xylene ...... 75 parts Dimethylformamide ...... 15 parts Sorpol 2680 ...... 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. ) Brand name) Mix the above uniformly to make an emulsion. In use, the above emulsion is diluted 10 to 10,000 times and sprayed so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

Formulation 4 Flowable compound of the present invention No4 ...... 25 parts Agrisol S-710 ...... 10 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000C ...... 0.5 parts (Anionic surfactant: Toho Kagaku) Product name: 1% Rhodopol water: 20 parts (Thickener: Lone Poulean Company product name) Water: 44.5 parts The above ingredients are mixed uniformly to make a flowable agent.

Formulation example 5 Flowable compound of the present invention No1 ...... 40 parts Agrisol S-710 …… 10 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000C …… 0.5 part (Anionic surfactant: Toho Kagaku) Product name: 1% Rhodopol Water: 20 parts (Thickener: Lone Poulean Company product name) Water: 29.5 parts Mix the above uniformly to make a flowable agent.

Formulation Example 6 Granules Compound of the present invention No3 …… 1 part Bentonite …… 55 parts Talc …… 44 parts After uniformly mixing and pulverizing the above, add a small amount of water and knead with stirring, kneading, extrusion granulator Granulate with and dry to make granules.

Further, the compound of the present invention may be mixed and applied with other kinds of herbicides, various insecticides, fungicides, synergists and the like at the time of preparation or spraying, if necessary.

Examples of the above-mentioned other types of herbicides include, for example, farm. Chemicals. Handbook (Farm Chemicals Handbook) 198
There are compounds listed in the 5-year edition.

The compound of the present invention can be applied to the control of various weeds in non-agricultural fields such as fields, paddy fields, orchards in fields other than agricultural and horticultural fields such as orchards, and its application dosage is Although there are differences depending on the time of application, method of application, target grass species, cultivated crops, etc., in general, an amount of active ingredient of about 0.005 to 10 kg per hectare is suitable.

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

Test Example-1 Herbicidal Effect Test by Soil Treatment 15 cm in height, 22 cm in width, and 6 cm in depth put sterilized diluvial soil in a plastic box, and then Novier, Crabgrass, Cyperus,
Cochleate chinensis, Japanese barley, dogwood, rice, corn, wheat, soybean, and cotton were mixed and sown, and after covering the soil for about 1.5 cm, the active ingredients were evenly sprayed on the soil surface to a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder of the above formulation example with water and spraying it over the entire surface with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the following criteria.

The results are shown in Table 16.

Some of the compounds of this invention are selective for certain crops.

Criteria 5 …… Weeding rate 90% or more (almost complete death) 4 …… Weeding rate 70 to 90% 3 …… Weeding rate 40 to 70% 2 …… Weeding rate 20 to 40% 1 …… Weeding rate 5 to 20 % 0 ... herbicidal rate 5% or less (almost no efficacy) However, the above-mentioned herbicidal rate was obtained by measuring the above-ground weed weight of the chemical-treated area and the above-ground weed weight of the untreated area by the following formula. It is a thing.

Test Example-2 Herbicidal effect test by foliar treatment 15 cm in length, 22 cm in width, 6 cm in depth and put in a sterilized diluvial soil in a plastic box, and then Novier, Crabgrass, Cyperus,
Seeds of dogwood, Japanese barley, dogwood, rice, corn, wheat, soybean, cotton, and beet were sown in spots and covered with about 1.5 cm of soil. 2 kinds of plants
When the ~ 3 leaf stage was reached, the active ingredient amount was evenly applied to the foliage so that the amount of the active ingredient became a predetermined ratio. The chemical solution for spraying was prepared by diluting the wettable powder of the above formulation example with water and spraying it over the entire surface of the foliage of various weeds with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria of Test Example-1. The results are shown in Table 17.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A01N 47/42 A 9159-4H 47/44 9159-4H C07D 403/14 233 7602-4C // C07D 401/04 233 7602-4C 403/04 233 7602-4C (C07D 401/14 213: 00 8217-4C 233: 00 9360-4C 239: 00) 8615-4C (C07D 401/04 213: 00 8217-4C 233 : 00) 9360-4C (72) Inventor Eiichi Oya 1 722, Tsuboi-cho, Funabashi-shi, Chiba Central Research Laboratory, Nissan Chemical Industry Co., Ltd. Company Biochemistry Research Institute (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Biochemistry Research Institute (72) Inventor Kenji Hattori Minami Saitama-Gun, Saitama Prefecture 1470 Shiraoka, Okamachi Osamu Masato Ikeda Examiner, Biochemical Research Institute, Nissan Chemical Industries, Ltd

Claims (2)

[Claims] 1. General formula (I): [Where Q is Indicates. [R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, a lower halogenated alkyl group, COOR ¹⁰ , S (O) _n R ¹¹ , NR ¹² R ¹³ , lower Alkoxy group, SO ₂ NR ⁸ R ⁹ , SO ² OR ¹¹ or optionally substituted phenyl group (substituents are halogen atom, nitro group, CO
It is selected from OR ¹⁰ , a lower alkoxy group or a lower alkyl group. ) Is shown. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower halogenated alkyl group, a nitro group, COOR ¹⁰ , S (O) _n R ¹¹ , a lower alkoxy group or may be substituted. A phenyl group (the substituent is selected from a halogen atom, COOR ¹⁰ , a nitro group, a lower alkoxy group or a lower alkyl group). R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. R ⁸ and R ⁹ each independently represent a hydrogen atom, a lower alkyl group or a phenyl group. R ¹⁰ represents a hydrogen atom or a lower alkyl group. R ¹¹ is a lower alkyl group, and n is an integer of 0, 1 or 2. R ¹² and R ¹³ each independently represent a hydrogen atom or a lower alkyl group. ] M shows the integer of 0, 1 or 2. R represents a hydrogen atom or a lower alkyl group. B and D are each independently a hydrogen atom, halogen atom, nitro group, lower alkyl group, allylalkyl group, lower alkoxy group, halogenated alkyl group, halogenated alkenyl group, lower alkoxyalkyl group, alkylcarbonyl group, COOR ¹⁴ , CONR ¹⁵ R ¹⁶ , S (O) _n R ¹⁷ , cyano group, NR
¹⁸ R ¹⁹ , SO ² NR ²⁰ R ²¹ , OH, optionally substituted benzoyl group (substituent is selected from halogen atom or lower alkyl group) or optionally substituted phenyl group (substituent is halogen Atom, nitro group, COOR ¹⁰ , lower alkoxy group or lower alkyl group). R ¹⁴ is a hydrogen atom, an optionally substituted lower alkyl group (the substituent represents a lower alkoxy group optionally substituted by OR ^10, halogen atom, halogenated lower alkoxy group, a cyano group, a phenoxy group, a lower alkoxycarbonyl Basis, NR
¹⁰ R ¹¹ , a lower cycloalkyl group, a lower alkylthio group or a lower alkylcarbonyl group. ), A lower alkenyl group, a halogenated lower alkenyl group, a lower alkynyl group, a halogenated lower alkynyl group, a lower cycloalkyl group or a benzyl group. R ¹⁵ represents a hydrogen atom, a lower alkyl group or a phenyl group. R ¹⁶ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group. R ¹⁷ represents a lower alkyl group, a lower alkoxy group, a phenyl group, a halogenated alkyl group, a lower alkenyloxy group or a lower alkynyloxy group. n is 0, 1 or 2
Indicates an integer. R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, a lower alkyl group, a lower alkylcarbonyl group or a lower alkylsulfonyl group. R ²⁰ and R ²¹ each independently represent a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group. T is Or Indicates. E represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkoxy group. G is Indicates. [X and Y are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxyalkyl group, a halogenated alkyl group, a lower halogenated alkoxy group, NR ²⁴ R ²⁵ , OCH (R ¹⁰ ) COOR ¹⁰ , COOR ¹⁰ ,
A cyclopropyl group, CH (OR ²⁶ ) ₂ , a lower alkylthio group or a lower halogenated alkylthio group is shown. R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a lower alkyl group or a lower alkoxy group. R ²⁶ represents a lower alkyl group. X ¹ and Y ¹ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a halogenated alkyl group or a lower alkoxy group. X ² represents a lower alkyl group, a lower alkylthio group or a lower alkoxy group, and Y ² represents a lower alkyl group. Z represents a nitrogen atom or C—R ²⁷ . R ²⁷ represents a hydrogen atom, a lower alkyl group, a lower halogenated alkyl group, a halogen atom, a lower alkoxy group or a 5-membered ring structure containing an oxygen atom together with Y or Y ¹ . X ³ represents a lower alkyl group, a lower alkoxy group, a lower alkoxyalkyl group or a halogen atom. Y ³ represents a lower alkyl group, a lower alkoxy group, a halogen atom, a monoalkylamino group or a dialkylamino group. Y ⁴ represents a cyano group, CO ₂ R ¹⁰ , a nitro group, S (O) _n R ¹¹ , an alkyl group or a halogenated alkyl group. Z ¹ represents a nitrogen atom or CH. X ⁴ and Y ⁵ each independently represent a lower alkyl group or a lower alkoxy group. W represents an oxygen atom, a sulfur atom or N—R ²⁸ . R ²⁸ represents a hydrogen atom or a lower alkoxy group. W ¹ represents an oxygen atom or a sulfur atom. R ²² represents a lower alkyl group. Az represents an imidazolyl, imidazolinyl, pyrazolyl, triazolyl or benzimidazolyl group which may be mono-, di- or tri-substituted by a halogen atom nitro group or a lower alkyl group. J is a lower alkyl group or (Q, R, m, B and D have the same meanings as described above). R ²³ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group. An imidazole sulfonamide derivative represented by: 2. General formula (I): [Where Q is Indicates. [R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group, a lower halogenated alkyl group, COOR ¹⁰ , S (O) _n R ¹¹ , NR ¹² R ¹³ , lower Alkoxy group, SO ₂ NR ⁸ R ₂ , SO ² OR ¹¹ or optionally substituted phenyl group (substituents are halogen atom, nitro group, CO
It is selected from OR ¹⁰ , a lower alkoxy group or a lower alkyl group. ) Is shown. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower halogenated alkyl group, a nitro group, COOR ¹⁰ , S (O) _n R ¹¹ , a lower alkoxy group or may be substituted. A phenyl group (the substituent is selected from a halogen atom, COOR ¹⁰ , a nitro group, a lower alkoxy group or a lower alkyl group). R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. R ⁸ and R ⁹ each independently represent a hydrogen atom, a lower alkyl group or a phenyl group. R ¹⁰ represents a hydrogen atom or a lower alkyl group. R ¹¹ is a lower alkyl group, and n is an integer of 0, 1 or 2. R ¹² and R ¹³ each independently represent a hydrogen atom or a lower alkyl group. ] M shows the integer of 0, 1 or 2. R represents a hydrogen atom or a lower alkyl group. B and D are each independently a hydrogen atom, halogen atom, nitro group, lower alkyl group, allylalkyl group, lower alkoxy group, halogenated alkyl group, halogenated alkenyl group, lower alkoxyalkyl group, alkylcarbonyl group, COOR ¹⁴ , CONR ¹⁵ R ¹⁶ , S (O) _n R ¹⁷ , cyano group, NR
¹⁸ R ¹⁹ , SO ₂ NR ²⁰ R ²¹ , OH, optionally substituted benzoyl group (substituent is selected from halogen atom or lower alkyl group) or optionally substituted phenyl group (substituent is halogen Atom, nitro group, COOR ¹⁰ , lower alkoxy group or lower alkyl group). R ¹⁴ is a hydrogen atom, an optionally substituted lower alkyl group (the substituent represents a lower alkoxy group optionally substituted by OR ^10, halogen atom, halogenated lower alkoxy group, a cyano group, a phenoxy group, a lower alkoxycarbonyl Basis, NR
¹⁰ R ¹¹ , a lower cycloalkyl group, a lower alkylthio group or a lower alkylcarbonyl group. ), A lower alkenyl group, a halogenated lower alkenyl group, a lower alkynyl group, a halogenated lower alkynyl group, a lower cycloalkyl group or a benzyl group. R ¹⁵ represents a hydrogen atom, a lower alkyl group or a phenyl group. R ¹⁶ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group. R ¹⁷ represents a lower alkyl group, a lower alkoxy group, a phenyl group, a halogenated alkyl group, a lower alkenyloxy group or a lower alkynyloxy group. n is 0, 1 or 2
Indicates an integer. R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, a lower alkyl group, a lower alkylcarbonyl group or a lower alkylsulfonyl group. R ²⁰ and R ²¹ each independently represent a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group. T is Or Indicates. E represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkoxy group. G is Indicates. [X and Y are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxyalkyl group, a halogenated alkyl group, a lower halogenated alkoxy group, NR ²⁴ R ²⁵ , OCH (R ¹⁰ ) COOR ¹⁰ , COOR ¹⁰ ,
A cyclopropyl group, CH (OR ²⁶ ) ₂ , a lower alkylthio group or a lower halogenated alkylthio group is shown. R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a lower alkyl group or a lower alkoxy group. R ²⁶ represents a lower alkyl group. X ¹ and Y ¹ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a halogenated alkyl group or a lower alkoxy group. X ² represents a lower alkyl group, a lower alkylthio group or a lower alkoxy group, and Y ² represents a lower alkyl group. Z represents a nitrogen atom or C—R ²⁷ . R ²⁷ represents a hydrogen atom, a lower alkyl group, a lower halogenated alkyl group, a halogen atom, a lower alkoxy group or a 5-membered ring structure containing an oxygen atom together with Y or Y ¹ . X ³ represents a lower alkyl group, a lower alkoxy group, a lower alkoxyalkyl group or a halogen atom. Y ³ represents a lower alkyl group, a lower alkoxy group, a halogen atom, a monoalkylamino group or a dialkylamino group. Y ⁴ represents a cyano group, CO ₂ R ¹⁰ , a nitro group, S (O) _n R ¹¹ , an alkyl group or a halogenated alkyl group. Z ¹ represents a nitrogen atom or CH. X ⁴ and Y ⁵ each independently represent a lower alkyl group or a lower alkoxy group. W represents an oxygen atom, a sulfur atom or N—R ²⁸ . R ²⁸ represents a hydrogen atom or a lower alkoxy group. W ¹ represents an oxygen atom or a sulfur atom. R ²² represents a lower alkyl group. Az represents a imidazolyl, imidazolinyl, pyrazolyl, triazolyl or benzimidazolyl group which may be mono-, di- or substituted by a halogen atom nitro group or a lower alkyl group. J is a lower alkyl group or (Q, R, m, B and D have the same meanings as described above). R ²³ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group. A herbicide containing one or more imidazole sulfonamide derivatives represented by the following as an active ingredient.