JPH04321671A - Carbamoyltriazole derivative and herbicide containing the derivative as active component - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to novel carbamoyltriazole derivatives, herbicides containing them as active ingredients, and intermediates thereof.

0002

[Prior Art] Conventionally, carbamoyltriazole derivatives have been described as active ingredients of herbicides in U.S. Pat. No. 3,952,001, U.S. Pat. It is described that it can be used as

0003

[Problems to be solved by the invention] However, these known triazole derivatives are not necessarily satisfactory because they have insufficient herbicidal efficacy and poor selectivity between crops and weeds. .

[0004] As a result of intensive research into carbamoyltriazole compounds for the purpose of developing compounds with excellent herbicidal activity, the present inventors have found that carbamoyltriazole derivatives with a specific structure have excellent herbicidal efficacy with few drawbacks as mentioned above. The present inventors have discovered that the present invention is a compound that exhibits excellent selectivity between crops and weeds, and has completed the present invention.

[0005]

[Means for solving the problem] According to the present invention, the general formula

[
0006

[Formula 7] [In the formula, R1 and R2 are the same or different and are a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lower haloalkyl group, a lower haloalkenyl group, a lower alkoxyalkyl group, a lower alkoxy group , represents a lower alkoxycarbonyl group, a lower alkoxycarbonylalkyl group, an aralkyl group, or an aryl group, or R1 and R2 together have 3 to 6 carbon atoms.
represents an alkylene chain (this alkylene chain may be substituted with a lower alkyl group), and X is a group

[0007]

embedded image Or, an optionally benzo-fused 5- or 6-membered heterocycle containing 1 to 4 nitrogen atoms bonded by N (provided that these rings are lower alkyl groups, lower haloalkyl groups, or aryl (optionally substituted with a group), provided that X is 1
-Excluding cases of pyrrolidyl group and 1-piperidyl group, where R3 represents an optionally substituted aryl group (excluding halogen substitution), an optionally substituted aralkyl group, and R4 is a hydrogen atom, lower alkyl group, lower alkenyl group, lower alkynyl group, lower haloalkyl group, lower haloalkenyl group, lower cyanoalkyl group, lower alkoxy group, lower alkoxyalkyl group, lower alkoxycarbonylalkyl group, benzyloxy group or phenylcarbonyl group, ] A carbamoyltriazole derivative represented by the following formula and a herbicide containing the same as an active ingredient are provided.

In the general formula [I], R1, R2, and X are groups

[0009]

In the case where R4 is a lower alkyl group, the lower alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, Examples include t-butyl, iso-butyl, sec-butyl, etc., lower alkenyl groups and lower alkynyl groups each have 2 to 5 carbon atoms, preferably 3 to 4 carbon atoms, and lower cycloalkyl groups include carbon atoms Number 3
Examples of the lower haloalkyl group include those having 2 to 4 carbon atoms, examples of the lower alkoxyalkyl group include those having 3 to 5 carbon atoms, and examples of the lower haloalkenyl group include those having 3 to 4 carbon atoms. Examples of lower alkoxy groups include those with 1 to 3 carbon atoms, lower alkoxycarbonyl groups include those with 2 to 4 carbon atoms, and lower alkoxycarbonylalkyl groups include those with 2 to 4 carbon atoms. Examples include those having 3 to 6 carbon atoms, examples of aralkyl groups include those having 5 to 8 carbon atoms, and examples of aryl groups include those having 5 to 6 carbon atoms.

[0010]

[0011]

In the case of [Chemical formula 10], examples of the aryl group in R3 include those having 4 to 6 carbon atoms, and this aryl group includes a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxycarbonyl group. 1 to 4 of the groups may be substituted. Further, examples of the aralkyl group in R3 include those having 5 to 8 carbon atoms, and this aralkyl group is substituted with 1 to 4 of a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, and a lower alkoxycarbonyl group. may have been done.

Examples of the 5- or 6-membered heterocycle containing 1 to 4 nitrogen atoms, which may be benzo-fused, are bonded through N in X, such as

[0013]

[Image Omitted] These heterocycles include lower alkyl groups,
It may be substituted with a lower haloalkyl group or an aryl group.

[0014]

[0015]

In the case where Examples of the lower alkoxyalkyl group include those having 3 to 5 carbon atoms, and examples of the lower alkoxycarbonyl alkyl group include those having 3 to 6 carbon atoms.

Specific examples of the compounds of the present invention represented by the general formula [I] are shown in Table 1, Table 2, Table 3, and Table 4 below.

[0017] The compound numbers will be referred to in the following description.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

[Table 8]

[0026]

[Table 9]

[0027]

[Table 10]

[0028]

[Table 11]

[0029]

[Table 12]

[0030]

[Table 13]

[0031]

[Table 14]

[0032]

[Table 15]

[0033]

[Table 16]

[0034]

[Table 17]

[0035]

[Table 18]

[0036]

[Table 19]

[0037]

[Table 20]

[0038]

[Table 21]

[0039]

[Table 22]

[0040]

[Table 23]

[0041]

[Table 24]

[0042]

[Table 25]

[0043]

[Table 26]

[0044]

[Table 27]

[0045]

[Table 28]

[0046]

[Table 29]

[0047]

[Table 30]

[0048]

[Table 31]

[0049]

[Table 32]

[0050]

[Table 33]

[0051]

[Table 34]

[0052]

[Table 35]

[0053]

[Table 36]

[0054]

[Table 37]

[0055]

[Table 38]

[0056]

[Table 39]

[0057]

[Table 40]

[0058]

[Table 41]

[0059]

[Table 42]

[0060]

[Table 43]

[0061]

[Table 44]

[0062]

[Table 45]

[0063]

[Table 46]

[0064]

[Table 47]

[0065]

[Table 48]

[0066]

[Table 49]

[0067]

Table 50 The carbamoyltriazole derivative represented by the general formula (I) of the present invention can be produced, for example, by the method shown below, but is not limited to these methods.

[0068] Method A

[0069]

embedded image [In the formula, X, R1, and R2 have the same meanings as in the above general formula [I], and A represents a halogen atom. ] General formula [I]
The compound of the present invention represented by the formula [II] and the carbamoyl halide represented by the general formula [III] are combined in the presence of a base, preferably in a solvent at a temperature range of 0°C to 160°C. It can be produced by reacting for 10 minutes to 24 hours. At that time, the amount of reagents used in the reaction is determined based on the triazole derivative [I
I] The carbamoyl halide [III] is 1 to 1.5 equivalents, and the base is 1 to 5 equivalents.

Examples of solvents include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as benzene, toluene, and xylene; chloroform, carbon tetrachloride, dichloroethane, chlorobenzene,
Halogenated hydrocarbons such as dichlorobenzene; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; Nitro compounds such as nitroethane and nitrobenzene Nitriles such as acetonitrile and isobutyronitrile; Tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine, and N-methylmorpholine; Acid amides such as N,N-dimethylformamide; dimethyl sulfoxide , sulfur compounds such as sulfolane; or mixtures thereof.

Examples of the base include organic salts such as pyridine, triethylamine, and N,N-diethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride; sodium methoxide, sodium Examples include alkali metal alkoxides such as ethoxides.

After completion of the reaction, the reaction solution is subjected to usual post-treatments such as addition of water, organic solvent extraction and concentration, and, if necessary, can be purified by operations such as chromatography and recrystallization. can.

[0073] Method B

[0074]

[I
] and B represents a leaving group. ] The compound of the present invention represented by the general formula [I''] is a compound represented by the general formula [I']
] and a carbamoyltriazole derivative represented by R
4B (general formula [IV]) in the presence of a base, preferably in a solvent at a temperature range of 0°C to 160°C for 10 minutes to 24 hours. that time,
The amount of reagents used in the reaction is 1 to 2 R4B[IV] per equivalent of carbamoyltriazole derivative [I'].
equivalent, the base is 1 to 5 equivalents.

Examples of R4B include alkyl halides, alkyl methanesulfonates, alkylbenzenesulfonates, alkyl para-toluenesulfonates, alkyl trifluoromethanesulfonates, dialkyl sulfates, and the like.

Examples of solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; ethers such as diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether; esters such as ethyl acetate;
Halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; Aromatic hydrocarbons such as benzene, toluene, and xylene; N,N-dimethylformamide,
Examples include polar solvents such as dimethyl sulfoxide, mixtures thereof, and mixtures of these solvents and water.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; metal hydrides such as sodium hydride.

After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as addition of water, organic solvent extraction and concentration, and, if necessary, can be purified by operations such as chromatography and recrystallization. can.

C method

[0080]

[I
], and Y represents a halogen atom. ]
The compound of the present invention represented by the general formula [I] is a compound of the present invention represented by the general formula [V
] A carbamoyl triazole derivative represented by the formula [VI] is reacted with an aryl halide or an aralkyl halide represented by the general formula [VI] in the presence of a base, preferably in a solvent in a temperature range of 0°C to 160°C for 10 minutes to 24 hours. It can be manufactured by At that time, the amount of reagents used for the reaction is carbamoyltriazole [V]1
The amount of the aryl halide or aralkyl halide [VI] is 1 to 2 equivalents, and the amount of the base is 1 to 5 equivalents.

Examples of solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; ethers such as diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether; esters such as ethyl acetate;
Halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; Aromatic hydrocarbons such as benzene, toluene, and xylene; N,N-dimethylformamide,
Examples include polar solvents such as dimethyl sulfoxide, mixtures thereof, and mixtures of these solvents and water.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; metal hydrides such as sodium hydride.

After the completion of the reaction, the reaction solution is subjected to usual post-treatments such as addition of water and extraction with an organic solvent and concentration, and if necessary, can be purified by operations such as chromatography and recrystallization. can.

Next, the present invention will be explained in more detail with reference to Examples.

[0085]

[Example 1] N-benzyl-(1,2,4-triazol-3-yl)sulfonamide (compound number 386) 4.15 g of benzylamine was added to 5.4 ml of triethylamine.
and dissolved in 150 ml of tetrahydrofuran, 1,2,
4-triazol-3-ylsulfonyl chloride6.
18 g was added little by little under ice-cooling, and the mixture was returned to room temperature and stirred for 3 hours. The solvent was distilled off, 100 ml of cold 1N hydrochloric acid was added, and the precipitated solid was collected by filtration and dried. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound. Yield 7.1
g (yield 81%) melting point 215-218°C.

[0086]

[Example 2] N-benzyl-{1-(diethylcarbamoyl)-1,2,4-triazol-3-yl}sulfonamide (compound number 3) N-benzyl-(1,2,4-triazol-3-yl) Dissolve 7.4 g of sulfonamide in 30 ml of pyridine, add 4.71 g of diethylcarbamoyl chloride,
Stirred at room temperature for 14 hours. Pyridine is distilled off under reduced pressure,
75 ml of 2N hydrochloric acid was added and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound.

Yield 7.34g (yield 70%) Melting point 94~
95℃

[0088]

[Example 3] N-proparagyl-N-benzyl {1-(
diethylcarbamoyl)-1,2,4-triazole-
3-yl}sulfonamide (Compound No. 199) 1.0 g of N-benzyl-(1,2,4-triazol-3-yl)sulfonamide was mixed with 8 m of dimethylformamide.
After adding 0.50 g of potassium carbonate and 0.32 ml of proparagyl bromide,
Stir for hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. This is n-
Recrystallization from hexane-ethyl acetate gave the title compound.

Yield 0.89g (yield 80%) Melting point 109
．． 5-110.5℃

[0090]

[Example 4] N-ethyl-N-phenyl-(1,2,4
-triazol-3-yl)sulfonamide (Compound No. 404) 4.77 g of N-ethylaniline and 5.5 g of triethylamine.
Dissolve 5 ml in 150 ml of tetrahydrofuran,
, 6.60 g of 2,4-triazol-3-ylsulfonyl chloride were added little by little under ice cooling, and the mixture was returned to room temperature and stirred for 3 hours. The solvent was distilled off, 100 ml of cold 1N hydrochloric acid was added, and the precipitated solid was collected by filtration and dried. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound.

Yield 6.75g (68%) Melting point 158-1
61℃

[0092]

[Example 5] Production of N-ethyl-N-phenyl {1-(diethylcarbamoyl)-1,2,4-triazol-3-yl}sulfonamide (Compound No. 205) N-ethyl-N-phenyl-( 1,2,4-triazole-3
-yl) sulfonamide 6.75g in pyridine 17ml
3.99 g of diethyl carbamoyl chloride dissolved in
was added and stirred at room temperature for 14 hours. Pyridine was distilled off under reduced pressure, 50 ml of 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. This is n-
Recrystallization from hexane-ethyl acetate gave the title compound.

Yield 7.40g (yield 79%) Melting point 101
．． 5-102.5℃

[0094]

[Example 6] Preparation of N-methyl-N-benzyl {1-(diethylcarbamoyl)-1,2,4-triazol-3-yl}sulfonamide (compound number 4) 50 g of 1,2,4-triazol-3-yl)sulfonamide was dissolved in 200 ml of pyridine, 28.1 g of diethylcarbamoyl chloride was added, and the mixture was stirred at room temperature for 14 hours. Pyridine was distilled off under reduced pressure, 500 ml of 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound.

Yield 55.6g (yield 80%) Melting point 73~
74℃

[0096]

[Example 7] N-3-trifluoromethylphenyl (1
,2,4-triazol-3-yl)sulfonamide (
Production of Compound No. 402) 4.81 g of 3-trifluoromethylaniline and 4.1 ml of triethylamine were dissolved in 40 ml of tetrahydrofuran, and 5.0 g of 1,2,4-triazol-3-ylsulfonyl chloride was slightly added under ice cooling. The mixture was added in portions, and the mixture was returned to room temperature and stirred for 3 hours. Distill the solvent and add 30ml of cold 1N hydrochloric acid.
1 was added, and the precipitated solid was filtered and dried. This is n-
Recrystallization from hexane-ethyl acetate gave the title compound. Yield 2.8g (yield 32%) Melting point 254-256.5℃

[0097]

[Example 8] Production of 3,5-dimethyl-(1,2,4-triazol-3-yl)sulfonylpyrazole (compound number 404) 1.9 g of 3,5-dimethylpyrazole and 2.9 ml of triethylamine were mixed in tetrahydrofuran. 40 ml, add 3.4 g of 1,2,4-triazol-3-ylsulfonyl chloride little by little under ice cooling, and return to room temperature.
Stir for hours. The solvent was distilled off, 30 ml of cold 1N hydrochloric acid was added, and the precipitated solid was filtered and dried. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound. Yield 2
．． 8g (yield 60%) Melting point 171-173.5℃

00
98]

[Example 9] N-3-trifluoromethylphenyl {1
-(diethylcarbamoyl)-1,2,4-triazol-3-yl}sulfonamide (compound number 67) N-3-trifluoromethylphenyl-(1,2,4-
2.56 g of triazol-3-yl)sulfonamide was dissolved in 10 ml of pyridine, 1.22 g of diethylcarbamoyl chloride was added, and the mixture was stirred at room temperature for 14 hours. Pyridine was distilled off under reduced pressure, 25 ml of 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound. Yield 3.07g (yield 90%) Melting point 146.5-148℃

0099

[Example 10] Production of 3,5-dimethyl{1-(diethylcarbamoyl)-1,2,4-triazol-3-yl)sulfonylpyrazole (Compound No. 322) 3,5
-dimethyl-(1,2,4-triazol-3-yl)
Dissolve 1.5 sulfonyl pyrazole in 7 ml of pyridine, add 0.94 g of diethylcarbamoyl chloride,
Stirred at room temperature for 14 hours. Pyridine is distilled off under reduced pressure,
20 ml of 2N hydrochloric acid was added and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. These were recrystallized from n-hexane-ethyl acetate to obtain the title compound. Yield 1.8g (yield 83%) Melting point 87-89℃

[0100]

[Example 11] N-methyl-N-3-trifluoromethylphenyl {1-(diethylcarbamoyl)-1,2,
Preparation of N-3-trifluoromethylphenyl-(1,2,4-
Dissolve 1.5 g of triazol-3-yl) sulfonamide in 10 ml of dimethylformamide, and add 0.0 g of potassium carbonate.
．． After adding 64 g and 0.82 g of methyl iodide to this, the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain crude crystals. This was recrystallized from n-hexane-ethyl acetate to obtain the title compound. Yield 1.38g (yield 89%) Melting point 71
．． 5-72℃

[0101]

[Example 12] N-t-butyl-N-benzyl {1-(
diethylcarbamoyl)-1,2,4-triazole-
3-yl}Sulfonamide (Compound No. 37) Production N
-t-butyl {1-(diethylcarbamoyl)-1,2
,4-triazol-3-yl}sulfonamide 0.7
g was dissolved in 3 ml of dimethylformamide, 0.34 g of potassium carbonate and 0.41 g of benzyl bromide were added thereto, and the mixture was stirred at 50° C. for 18 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate, then the solvent was distilled off and the remaining oil was purified by silica gel chromatography to obtain the title compound. Yield: 0.24 g (yield: 27%) Melting point: 87 to 88°C Compounds shown in Table 5 below were synthesized by the same method. The NMR data of those compounds are shown below.

[0102]

[Table 51]

[0103]

[Table 52]

[0104]

[Table 53]

[0105]

[Table 54]

[0106]

[Table 55]

[0107]

[Table 56]

[0108]

[Table 57]

[0109]

[Table 58]

[0110]

[Table 59]

[0111]

[Table 60]

[0112]

Table 61 The herbicide of the present invention comprises a novel carbamoyltriazole derivative represented by the above general formula [I] as an active ingredient. When the compound represented by the general formula [I] of the present invention is used as a herbicide, it is mixed with a carrier, a diluent, an additive, an auxiliary agent, etc. by a method known per se, and then used as a pesticide. Pharmaceutical forms, such as powders, granules,
It is used by preparing wettable powders, emulsions, aqueous solutions, flowable preparations, etc. In addition, other agricultural chemicals such as fungicides, insecticides, acaricides, other herbicides, plant growth regulators, fertilizers, soil conditioners, etc. can be mixed or used in combination. In particular, when used in combination with other herbicides, it is possible to not only reduce the amount of chemicals used and save labor, but also to expand the herbicidal spectrum due to the synergistic action of both herbicides, and to achieve even higher effects due to the synergistic action. .

Specific examples of other herbicides that can be used in combination with the compound of the present invention represented by the general formula [I] include, for example, carbamate herbicides: methyl 3,4-dichlorophenyl carbamate (general Name: SWEP), isopropyl 3-chlorophenyl carbamate (generic name: Chlorprofum, Ch
lorpropham), S-(p-chlorobenzyl)diethylthiocarbamate (generic name: Benthiocarb)
, S-ethyl-N,N-hexamethylenethiocarbamate (common name: Molinate), S-(
1-Methyl-1-phenylethyl) piperidine-1-carbothioate (generic name: dimepiperate, Dimep
iperate), S-benzyl-N-ethyl-N-(1,2-dimethylpropyl)thiol carbamate (generic name: Esprocarb), [(methoxycarbonyl)amino]phenyl (3-methylphenyl) carbamate (generic name: Phenmedipham), ethyl 3-phenylcarbamoyloxyphenyl carbamate (generic name: Desmediph)
am), O-(3-tert-butylphenyl)-N-
(6-Methoxy-2-pyridyl)-N-methyl-thiocarbamate (generic name: pyributicarb, Pyribut
ycarb), etc.; Urea herbicides: 1-(α,α-dimethylbenzyl)-3-(4-methylphenyl)urea (generic name: Dymron)
), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (generic name: Diuron), 1,
1-dimethyl-3-(α,α,α-trifluoro-m-
tril) urea (generic name: fluometuron, Fluom
eturon), 3-[4-(4-chlorophenoxy)phenyl]-1,
1-dimethylurea (generic name: chloroxuron, Chl
oroxuron), 3-(3,4-dichlorophenyl)-1-methoxy-1
-Methylurea (generic name: Linuron)
), 3-(4-chlorophenyl)-1-methoxy-1-
Methylurea (generic name: Monolinyuron, Monoli
3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea (generic name: Chlorbromron), 1-(α,α-dimethylbenzyl)-3-(2-chloro Benzyl) urea (code number: JC-940), etc.; Amide herbicide: 2-chloro-2',6'-diethyl-N-methoxymethylacetanilide (generic name: Alachlor, Alach
lor), N-butoxymethyl-2-chloro-2',6
'-diethylacetanilide (generic name: butachlor,
Butachlor), 2-chloro-2',6'-diethyl-N-(2-propoxyethyl)acetanilide (generic name: bretilachlor, Pretilachlor), 2-chloro-N-isopropylacetanilide (generic name: propachlor, Propachlor), 3', 4
'-Dichloropropionanilide (generic name: Propanil), N-(1,1-dimethylbenzyl)-2-bromo-te
rt-butylacetamide (generic name: bromobutide, B
romobutide), 2-benzothiazol-2-yloxy-N-methylacetanilide (generic name: mefenacet, Mefena
set), N,N-dimethyldiphenylacetamide (
Generic name: Diphenamide), N-
[2'-(3'-methoxy)-thienylmethyl]-N-
Chloroaceto-2,6-dimethylanilide (Code number: NSK-850), 2',6-diethyl-N-[(2-cis-bitenooxy)methyl]-2-chloroacetanilide (Code number:
KH-218) etc.; dinitrophenyl herbicide: 4,6-dinitro-o-cresol (generic name: DNOC
), 2-tert-butyl-4,6-dinitrophenol (generic name: Dinoterb), 2-se
c-Butyl-4,6-dinitrophenol (generic name: Dinoseb), N,N-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (generic name: Dinitramine) , α,α,α-trifluoro-2,6-dinitro-N,N
-dipropyl-p-toluidine (generic name: trifluralin), 4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (generic name: nitralin)
in), N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine (generic name: pendimethalin,
Phenoxy herbicides: 2,4-dichlorophenoxyacetic acid (generic name: 2,4-D
), 2,4,5-trichlorophenoxyacetic acid (common name: 2,
4,5-T), 4-chloro-o-tolyloxyacetic acid (common name: MCPA
), 4-(4-chloro-o-tolyloxy)butyric acid (common name: MCPB), 2,4-dichlorophenoxybutyric acid (common name: 2,4-D
B), 2-(4-chloro-o-tolyloxy)propionic acid (
Generic name: Mecoprop), 2-(2
,4-dichlorophenoxy)propionic acid (generic name: dichloroprop), (RS)-
2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid (generic name: Diclof,
op) and its esters, (RS)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionic acid (generic name: Fluazifop) and its esters, 2-(2, 4-dichloro-3-methylphenoxy)
Propionanilide (generic name: Cromeprop, Cro
meprop), S-ethyl-4-chloro-2-methylphenoxythioacetate (common name: phenothiol, Phenothi
ol), 2-(2-naphthoxy)propionanilide (
Generic name: Naproanilide)
etc; Carboxylic acid herbicide: 2,2-dichloropropionic acid (generic name: Darapon, D
alapone), trichloroacetic acid (common name: TCA), 2,3,6-trichlorobenzoic acid (common name: 2,3,6
-TBA), 3,6-dichloro-o-anisic acid (common name:
Dicamba), 3-amino-2,5-dichlorobenzoic acid (generic name: Chloramben), etc.; Organophosphorus herbicide: O-ethyl-O-(2-nitro-5-methylphenyl)
-N-sec-butylphosfluoramide thioate (
Common name: Butamifo), O, O-
Diisopropyl-S-(2-benzenesulfonylaminoethyl)phosfluorodithioate (generic name: SAP
), S-(2-methylpiperidin-1-yl)carbonylmethyl-O,O-dipropylphosfluorodithioate (
Benzonitrile herbicides: 2,6-dichlorobenzonitrile (common name: dichlorobenil), 3,5-dibromo-4-hydroxylbenzonitrile (common name: Piperophos), etc.;
Generic name: Bromoxynil, 4
-Hydroxy-3,5-diiodobenzonitrile (generic name: Ioxynil), etc.; diphenyl ether herbicide: 2,4-dichlorophenyl-4-nitrophenyl ether (generic name: Nitrofen) ,2,
4,6-Trichlorophenyl-4'-nitrophenyl ether (common name: chlornitrophen, Chlorni
trophen), 5-(2,4-dichlorophenoxy)-3-methoxy-
4-nitrophenyl ether (generic name: chlormethoxynil), methyl 5-(2
, 4-dichlorophenoxy)-2-nitrobenzoate (generic name: Bifenox), 4-nitrophenyl-α,α,α-trifluoro-2-nitro-p-tolyl ether (generic name: fluorodiphen) ,F
fluorodifen), 2-chloro-4-trifluoromethylphenyl-3-ethoxy-4-nitrophenyl ether (common name: Oxyfluorfen), 5-(2
-chloro-α,α,α-trifluoro-p-tolyloxy)-2-nitrobenzoic acid (generic name: acifluorfen), etc.; triazine herbicide: 4-amino-3-methyl-6- Phenyl-1,2,4-
Triazin-5(4H)-one (generic name: Metamitron), 4-amino-6-tert-butyl-3-methylthio-
1,2,4-triazin-5(4H)-one (common name:
Metribuzin), 2-chloro-
4,6-bis(ethylamino)-1,3,5-triazine (generic name: Simazine), 2-chloro-4-ethylamino-6-isopropylamino-1,
3,5-triazine (generic name: atrazine, Atraz
ine), 2,4-bis(ethylamino)-6-methylthio-1,
3,5-triazine (generic name: simetrine, Simet
oryne), 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine (generic name: promethrin, P
rometryne), 2-methylthio-4-ethylamino-6-(1,2-dimethylpropylamino)-1,3,5-triazine (generic name: Dimetametrine)
etc; Sulfonylurea herbicide: 2-chloro-N-[4-methoxy-6-methyl-1,3
,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide (generic name: chlorsulfuron, C
hlorsulfuron), methyl 2-{[((4,6-dimethoxypyrimidine-2
-yl)aminocarbonyl)aminosulfonyl]methyl}benzoate (generic name: bensulfuron-methyl, Be
nsulfuron methyl), ethyl 2-[(
(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl)aminosulfonyl]benzoate (generic name: chlorimuron ethyl, Chlorimuron
ethyl), ethyl 5-[((4,6-dimethoxypyrimidine-2-
yl)aminocarbonyl)aminosulfonyl]-1-methyl-1H-pyrazole-4-carboxylate (generic name: pyrazosulfuronethyl, Pyrazosulfur)
ron ethyl), 2-(2-methoxyethoxy)
-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide (generic name: Synosulfuron, Synosulfur)
ron), 2-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]imidazo[1
, 2-a] pyridine-3-sulfonamide (code number: TH-9l3), etc.; diazine herbicide: 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl-p −Toluenesulfonate (
Generic name: Pyrazolate, 1,
3-dimethyl-4-(2,4-dichlorobenzoyl)-
5-phenacyloxypyrazole (generic name: pyrazoxyfen), 1,3-dimethyl-4-(2,4-dichloro-3-methylbenzoyl)-
5-(4-methylphenaciloxy)pyrazole (generic name: Benzofenap), etc.; Other herbicides: 3,6-dichloropyridine-2-carboxylic acid (generic name:
Clopyralid), 4-amino-
3,5,6-trichloropyridine-2-carboxylic acid (generic name: Picloram), 5-amino-
4-Chloro-2-phenylpyridazin-3(2H)-one (generic name: Chloridazon)
, 3-cyclohexyl-1,5,6,7-tetrahydrocyclopentapyrimidine-2,4(3H)-dione (generic name: Lenacil), 5-bromo-3-sec-butyl-6-methyluracil (generic name (Bromacil), 3-te
rt-Butyl-5-chloro-6-methyluracil (generic name: Terbacil), 3-isopropyl-(1H)-2,1,3-benzothiadiazine-4 (
3H)-one 2,2-dioxide (generic name: Bentazone), N-1-naphthylphthalamic acid (generic name: Naptalam), S,S-dimethyl-2-(difluoromethyl)-4- (
2-methylpropyl)-6-(trifluoromethyl)-
3,5-pyrimidinecarbothioate (code number: M
on-72), 2,3-dihydro-3,3-dimethyl-5-benzofuranylethanesulfonate (generic name: benfuresate,
Benfuresate), 5-tert-butyl-3-(2,4-dichloro-5-
isopropoxyphenyl)-1,3,4-oxadiazol-2(3H)-one (common name: oxadiazone, O
xadiazon), exo-1-methyl-4-(1-methylethyl)-2-
[(2-methylphenyl)methoxy]-7-oxabicyclo[2,2,1]heptane (Code number: SKH-3
01), etc.

[0114] As the carrier or diluent used in the formulation of the herbicide of the present invention, solid or liquid carriers commonly used in agriculture are used. Solid carriers include clays such as kaolinite group, montmorillonite group, or apattalgite group, talc, mica, waxite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium coal, and phosphorous lime. Inorganic substances such as , zeolite, silicic anhydride, and synthetic calcium silicate; Vegetable organic substances such as soybean flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, and crystalline cellulose; Coumaron resin, petroleum resin, alkyd resin, Synthetic or natural polymer compounds such as polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, cobal gum, and dammar gum; other examples include waxes such as carnauba wax and beeswax, and urea. Suitable liquid carriers include, for example, kerosene, mineral oil, spindle oil,
Paraffinic or naphthenic hydrocarbons such as white oil; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, methylnaphthalene; dioxane,
Ethers such as tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, Alcohols such as n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether; polarity such as dimethylformamide, dimethyl sulfoxide, etc. Examples include a solvent or water.

In addition, surfactants and other auxiliary agents may be used for the purposes of emulsifying, dispersing, wetting, spreading, binding, adjusting disintegrability, stabilizing the active ingredient, improving fluidity, preventing rust, etc. of the compound of the present invention. You can also do that. Examples of surfactants used include nonionic, anionic, cationic, and zwitterionic compounds, but typically nonionic and/or anionic compounds are used. is used.

Suitable nonionic surfactants include, for example, compounds obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol, isooctylphenol,
Compounds in which ethylene oxide is polymerized and added to alkylphenols such as nonylphenol, compounds in which ethylene oxide is polymerized and added to alkylnaphthols such as butylnaphthol and octylnaphthol, and ethylene oxide is polymerized and added to higher fatty acids such as palmitic acid, stearic acid, and oleic acid. Examples include compounds obtained by polymerizing and adding ethylene oxide to higher fatty acid esters of polyhydric alcohols such as sorbitan, and compounds obtained by polymerizing and adding ethylene oxide and propylene oxide.

Suitable anionic surfactants include, for example, alkyl sulfate ester salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; Sulfonate salts; aryl sulfonate salts such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate;

Furthermore, the herbicide of the present invention may contain polymers such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, etc., in order to improve the properties of the preparation and increase the herbicidal effect. Compounds and other adjuvants can also be used in combination.

The above-mentioned carriers and various auxiliary agents are used alone or in combination as appropriate depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

[0120] The content of the compound of the present invention (active ingredient) in the various formulations thus obtained varies depending on the formulation, but it is usually 0.1 to 99% by weight, particularly 1% by weight. -80% by weight is most preferred.

[0121] In the case of a powder, the active ingredient compound is usually contained in an amount of 1 to 25% by weight, and the remainder is a solid carrier.

[0122] In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 25 to 90% by weight, and the remainder is a solid carrier, a dispersion wetting agent, and if necessary, a protective colloid agent, an antifoaming agent, etc. are added. It will be done.

[0123] In the case of granules, for example, the active ingredient compound is usually contained in an amount of 0.01 to 20% by weight, with the remainder being mostly solid carriers, surfactants, and the like. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle size is about 0.
2 to 1.5 mm.

[0124] In the case of an emulsion, for example, it usually contains 5 to 30% by weight of the active ingredient compound, and about 5 to 2% by weight of the active ingredient compound.
0% by weight of emulsifier is included, the balance is liquid carrier, and rust inhibitors are added as needed.

[0125] In the case of a flowable agent, for example, it usually contains 5 to 50% of the active ingredient compound, and 3 to 1% of the active ingredient compound.
It contains 0% by weight of a dispersion wetting agent, and the remainder is water, with protective colloids, preservatives, antifoaming agents, etc. added as necessary.

The novel carbamoyltriazole derivative of the present invention can be used as a compound of general formula [I] or in any preparation form as described above.

The herbicide of the present invention can be applied to exterminate or control various weeds growing in rice fields and fields from before their emergence to the growing season. The application amount is 0.001 to 5 per ha as the amount of the compound represented by the general formula [I] (amount of active ingredient).
The amount is about 0.01 to 1.2 kg, preferably about 0.01 to 1.2 kg, and can be selected as appropriate depending on the type of target weed, growth stage, application site, application time, weather, etc.

Next, several embodiments of formulation examples using the compounds of the present invention will be shown. "Parts" in the following formulation examples are based on weight.

Formulation Example 1 (Granules) Compound No. 4
Part 1 bentonite
Part 54 Talc

40 parts Sodium dodecylbenzenesulfonate 2 parts Sodium ligninsulfonate
Part 2 Polyoxyethylene styryl phenyl
ether
After thoroughly mixing at least 1 part, an appropriate amount of water was added and kneaded, followed by granulation using a granulator to obtain 100 parts of granules.

Formulation example 2 (hydrating powder) Compound No. 25
Part 20 Diatomaceous earth

60 parts white carbon
1
5 parts Sodium ligninsulfonate
3 parts Sodium dodecylbenzenesulfonate Mix 2 parts or more and mix and grind uniformly with a kneader to make a wettable powder of 10 parts.
I got 0 copies.

Formulation Example 3 (Emulsion) Compound No. 27
30 parts xylene

55 parts cyclohexanone

10 parts Calcium dodecylbenzenesulfonate
Part 3 Polyoxyethylene styryl phenyl ether
Two or more parts were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Drugs using the compounds of the present invention were prepared according to the above-mentioned formulation examples.

[0133]

Effects of the Invention The carbamoyltriazole derivative represented by the general formula [I] of the present invention is a novel compound described at the end of the literature. The compound represented by the general formula [I] of the present invention may have a structure in which an N-alkyl-N-sulfamoyl group is bonded to the 3-position of the 1-carbamoyl-1,2,4-triazole ring. It is thought that this carbamoyltriazole derivative exhibits excellent herbicidal performance due to its structural characteristics.

The compounds and herbicides of the present invention can control various weeds growing in agricultural land from the pre-emergence stage to the growing stage. For example, paddy field weeds such as field weeds, scallops, water holly, japonica, azaena, water chickweed, kikashigusa, pine snail, and cyperus, as well as snail grass, foxtail grass, cypress, sycamore, sycamore, chickweed, polygonum, etc.
Amaranths, Japanese crocodile, Japanese whiteweed, American goldenrod, Japanese fir tree, ragweed, shepherd's purse, ash tree, sagebrush,
It can control various weeds in the fields such as turmeric and buckwheat. Furthermore, it can be used not only in rice fields and fields, but also in orchards, mulberry gardens, lawns, and non-agricultural lands.

Next, the effect of the herbicide of the present invention will be explained with reference to test examples.

Test Example 1 (Paddy soil treatment) Area 1/500
Fill a 0 are Wagner pot with paddy soil mixed with an appropriate amount of chemical fertilizer, transplant 3 plants (2 plants 1 plant) of 2-leaf stage paddy rice (variety: Koshihikari) that were grown in a greenhouse in advance, and Seeds of , Japanese cypress, azalea, and cypress were sown.

Three days after transplanting paddy rice and sowing weeds, the compounds shown in Tables 6, 7, and 8 were prepared into granules according to Formulation Example 1, and treated with the active ingredient at 100 g/ha. The herbicidal effect and the degree of chemical damage were investigated 30 days after the chemical treatment according to the following criteria. The results are shown in Table 6, Table 7, and Table 8.

Evaluation criteria for weeding effect (11 levels) Weeding effect: In untreated area
Weed killing rate against chemical damage treatment plot (
%) Drug damage rate (%)
0 0 1 Over 0 ~ 10 or less
Same as left 2 Over 10 ~ 20 or less”
3 Over 20~30 or less
” 4 Over 30~
40 or less ” 5
Over 40 ~ 50 or less
” 6 Over 50 ~ 6
0 or less ” 7
Over 60 ~ 70 or less
” 8 Over 70 ~ 80 or less ” 9 8
Over 0~90 or less”
10 Over 90 ~ 100 or less
”

[0139]

[Table 62]

[0140]

[Table 63]

[0141]

[Table 64] Test Example 2 (Paddy growing season treatment) A Wagner pot with an area of 1/5000 are was filled with paddy soil mixed with an appropriate amount of chemical fertilizer, and two-leaf stage paddy rice (variety: Koshihikari) 3 plants (2
This 1st strain) was transplanted, and seeds of Japanese wildflower, Japanese cypress, Japanese azalea, and Japanese cypress were sown.

[0142] After 14 days of paddy rice transplantation and weed sowing, Table 9,
Each compound shown in Table 10 was prepared into granules according to Formulation Example 1, and treated with the active ingredient at 300 g/ha. The herbicidal effect and the degree of chemical damage were investigated according to the standards of Test Example 1 30 days after the chemical treatment.

[0143] The results are shown in Table 9, Table 10, Table 11, and Table 12.
Shown below.

[0144]

[Table 65]

[0145]

[Table 66]

[0146]

[Table 67]

[0147]

[Table 68]

[Chemical formula 16]

Claims (3)

[Claims] [Claim 1] General formula [Formula 1] [In the formula, R1 and R2 are the same or different and are a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lower haloalkyl group, a lower haloalkenyl group, a lower It represents an alkoxyalkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, a lower alkoxycarbonylalkyl group, an aralkyl group, or an aryl group, or R1 and R2 taken together have 3 to 6 carbon atoms.
represents an alkylene chain (this alkylene chain may be substituted with a lower alkyl group), and X is a group [Formula 2] or a benzo-fused group containing 1 to 4 nitrogen atoms bonded by N. a 5- or 6-membered heterocycle (these rings may be substituted with a lower alkyl group, a lower haloalkyl group, or an aryl group), provided that X is 1-
Except for pyrrolidyl group and 1-piperidyl group, R3 represents an optionally substituted aryl group (excluding halogen substitution) or an optionally substituted aralkyl group, and R4 is a hydrogen atom or a lower alkyl group. , represents a lower alkenyl group, lower alkynyl group, lower haloalkyl group, lower haloalkenyl group, lower cyanoalkyl group, lower alkoxy group, lower alkoxyalkyl group, lower alkoxycarbonylalkyl group, benzyloxy group or phenylcarbonyl group, ] A carbamoyltriazole derivative represented by: [Claim 2] General formula [Formula 3] [In the formula, R1 and R2 are the same or different and are a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lower haloalkyl group, a lower haloalkenyl group, a lower It represents an alkoxyalkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, a lower alkoxycarbonylalkyl group, an aralkyl group, or an aryl group, or R1 and R2 taken together have 3 to 6 carbon atoms.
represents an alkylene chain (this alkylene chain may be substituted with a lower alkyl group), and X is a group [Image Omitted] or a benzo-fused group containing 1 to 4 nitrogen atoms bonded by N. a 5- or 6-membered heterocycle (however, these rings may be substituted with an alkyl group, a haloalkyl group or an aryl group), except when X is a 1-pyrrolidyl group or a 1-piperidyl group, Here, R3 represents an optionally substituted aryl group (excluding halogen substitution) or an optionally substituted aralkyl group, and R4
is a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower cyanoalkyl group, a lower alkoxy group, a lower alkoxyalkyl group, a lower alkoxycarbonylalkyl group,
A herbicide characterized by containing a carbamoyltriazole derivative represented by ], which represents a benzyloxy group or a phenylcarbonyl group, as an active ingredient. Claim 3: General formula: [Formula 5] [wherein, represents a ring (however, these rings may be substituted with an alkyl group, a haloalkyl group or an aryl group), except when X is a 1-pyrrolidyl group or 1-piperidyl, where R3 is substituted R4 represents an optional aryl group (excluding halogen substitution) or an optionally substituted aralkyl group;
is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, a lower haloalkenyl group, a lower cyanoalkyl group, a lower alkoxy group, a lower alkoxyalkyl group, a lower alkoxycarbonyl group,
A triazole derivative represented by ], which represents a benzyloxy group or a phenylcarbonyl group.