JPH01216902A - herbicide composition - 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] Technical field The present invention relates to herbicidal compositions.

More specifically, the present invention relates to the formula CI), where R and R each represent a lower alkyl group, R'' represents a hydrogen atom or a lower alkyl group, and X represents a hydrogen atom or a halogen atom. 2-nitro-5 represented by
-One or more compounds selected from (substituted pyridyloxy)benzohydroxymic acid derivatives and 1,1'-dimethyl-
The present invention relates to a herbicidal composition containing 4,4'-bipyridinium dichloride (hereinafter sometimes abbreviated as paraquat) as an active ingredient.

The herbicidal composition of the present invention is a non-selective foliar treatment type herbicide that has an effective pear-type effect with reduced paraquat, has an extremely broad herbicidal spectrum, and has a high synergistic herbicidal effect.

PRIOR ART One of the active ingredients of the herbicidal composition of the present invention is represented by the general formula (I), where R and R1 each represent a lower alkyl group; % R'' represents a hydrogen atom or a lower alkyl group; The 2-nitro-5-(substituted pyridyloxy)benzohydroxymic acid derivative represented by - Filed earlier as No. 173888.
Ru.

1,1'-dimethyl-4,4'-bipyridinium chloride (hereinafter sometimes abbreviated as paraquat), which is another component used in the present invention, is disclosed in Dutch Painting Patent No. 660.
It is a known monster as described in the specification of No. 3346, Japanese Patent Publication No. 43-29140, etc.

The problem that the invention seeks to solve Paraquat is already known as a useful non-selective herbicide that treats foliage, but unfortunately it is highly acutely toxic and must be used with extreme caution to prevent accidents. Although countermeasures are necessary, unexpected accidents occur frequently. Therefore, there is a strong need to reduce the effective dose of paraquat when used alone.

Furthermore, paraquat has a narrow herbicidal spectrum and is less effective against important weeds such as Polygonaceae. In addition, paraquat has a very short weed control period, and the number of times the pesticide must be used is increased, resulting in problems such as an increase in the amount of pesticide residue in the soil and an increase in the cost of using the herbicide.

Effects of the Invention The herbicide composition of the present invention is a non-selective herbicide that treats foliage and reduces the effective use of baraquat to 11-wide. Moreover, the effective fecal dosage of the compound represented by the general formula CI) used in combination is extremely low, and synergistically exhibits an excellent herbicidal effect. Furthermore, the herbicidal composition of the present invention has a wide herbicidal spectrum and exhibits strong activity against weeds of the Polygonaceae family, which are problem weeds for which paraquat alone has poor activity.

In addition, the period of weed control is longer than that of paraquat alone, reducing the number of times pesticides are used.

DETAILED DESCRIPTION OF THE INVENTION The novel compound represented by the general formula (I) used in the present invention is described in detail in the specification of Japanese Patent Application No. 173888/1988, but the main part thereof is as follows. That's right.

Examples of the halogen atom of X in the pyridylphenyl ether derivative represented by the general formula <1) include fluorine, chlorine, bromine, and iodine. Among these, fluorine and chlorine are preferred.

As the lower alkyl group in 81% R2 and R,
A lower alkyl group having 1 to 5 carbon atoms is preferred, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, S-butyl, i-butyl, n-amyl, and the like.

The compound represented by the above general formula (I) may be a stereoisomer (
syn type and anti type) and optical isomer forms, and these isomeric forms of adducts of general formula (I) are:
It is to be understood that all such matters are within the scope of the present invention.

Among these examples, preferred examples of adducts of general formula (r) include compounds in which R'' is a methyl group, R' is a hydrogen atom or a methyl group, and R is a lower alkyl group of C, -Cs. can be mentioned.

The compound represented by the formula (I) can be prepared, for example, by the method shown below.

OR' Lull) OR" (It) [wherein, X, R1, R2 and R have the same meanings as described above for general formula (1), and X" is
0802R'(R'' represents a substituted or unsubstituted alkyl group, phenyl group, or alkoxy group)] According to this embodiment, 2-2) rho-5-(substituted pyridyloxy)benzoic acid (III) is The hydroxamic acid derivative (II) can be obtained by converting the compound into an acid chloride using, for example, thionyl chloride, and then reacting it with 0-substituted hydroxylamines in, for example, an organic solvent in the presence of a base.

In the reaction, the amount I/i of thionyl chloride to be used can be appropriately selected and changed, but it is, for example, 1 to 10 with respect to the compound of formula (m).
Examples include amounts used such as equivalent amounts. The reaction temperature can also be selected as appropriate, for example, from room temperature to 8oC. In the reaction between the formed acid chloride and the 0-substituted hydroxylamine, the amount of the 0-substituted hydroxylamine to be used can be selectively changed, for example, from 1 to 3. The amount of the base can also be selected appropriately, for example, 1 to 3 equivalents.

At this time, the reaction temperature may be, for example, from room temperature to 100°C.

Examples of solvents used include aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran and dioxane; one or more organic solvents such as acetone: acetonitrile; dimethylformamide; dimethyl sulfoxide; An example is a mixed solvent of these solvents and water.

Examples of the base include pyridine, triethylamine, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate.

〇-Substituted-2-nitro-5-(substituted pyridyloxy)benzohydroxymic acid derivative (II
) and alkylating agent ([V) also #1CH2N! 't Hydroxymic acid derivative used in the herbicide of the present invention by reacting in an organic solvent in the presence or absence of a base <r>'its
can be built.

The reaction is to react with adduct (11) with adduct (III) or C
H2N, for example, 1 to 3 molar equivalents, preferably /fi1 to
Using 1.5 mol, for example, under water cooling or at the reflux temperature of the solvent, preferably at room temperature to around 80°C, 0.
．． It can be carried out under conditions such as 5 to 20 hours. Solvents used in this reaction include, for example, alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone; acetonitrile: dimethylformamide; dimethyl sulfoxide. Examples include organic solvents such as; and mixed solvents of these solvents and water.

Examples of the base used in the above reaction include pyridine, triethylamine, sodium hydroxide, potassium hydroxide,
Examples include sodium carbonate, potassium carbonate, sodium ethylate, and sodium hydride. Addition of deoxidizing agent (
For example, 1 to 3 equivalents, preferably 1 to 1.
5 equivalents can be used and the reaction can be carried out in good yield, which is preferred.

Also, using CH,N,t- as the alkylating agent, there is no need to use a base when carrying out this reaction.

In addition, if the reaction is carried out in a two-phase system, 1. In the case where the reaction is carried out in a two-phase system, interphase salts such as quaternary ammonium salts such as tetramethylammonium bromide, tetrabutylammonium bromide, benzyltributylammonium bromide, and quaternary phosphonium salts such as tetraphenylphosphonium bromide may be used. Opening the catalyst with a compound (
IV), for example, 1 to 50 wt, preferably 5 to 50 wt.
It can be done using a 30wt wound.

After the reaction is completed, the compound represented by general formula (1) can be isolated by, for example, pouring the reaction mixture into water and treating it with conventional methods such as extraction with an organic solvent, P4 crystallization, column chromatography, etc. Can be done.

Next, preparation examples of the compound represented by the general formula U) will be described.

@Example 1. [Methyl 0-methoxycarbonylmethyl 5
-Production of (3-chloro-5-trifluoro-amethyl-2-pyridyloxy)-2-nitrobenzohydroxymate (compound A32) 5-(3-chloro-5-)IJfluoromethyl-2-pyridyloxy) -2-Nitrobenzoic acid 36°2t (0.10 mol) is dissolved in t-thionyl chloride 36.2- and heated under reflux for 1.5 hours. Excess thionyl chloride is distilled off to obtain acid chloride.

Aminooxyacetic acid methyl ester 10.59 (0°1
mole), triethylamine 10.1 ? (0.1 mol), to a solution of dry ether 300-1, the previously obtained ether 150-solution of the acid chloride was added dropwise over about 20 minutes while stirring under water cooling. Thereafter, the mixture was stirred for 30 minutes under water cooling and for 1.5 hours at room temperature. The reaction solution was poured into 300 ml of ice water, extracted three times with 200 ml of ethyl acetate, washed with saturated brine, and dried over magnesium sulfate.

After filtration with a desiccant, the solvent was distilled off and the resulting solid was recrystallized from triene to give methoxycarbonylmethyl 5-(
3-Chloro-5-trifluoromethyl-2-pyridyloxy)-2-nitrobenzohydroxamate 37.2
f was obtained (yield 82.7%).

37.2 of the hydroxamate obtained above was dissolved in a mixed solvent of t f ether 70-, tetrahydro 7-ran 70-, ML, water-cooled with stirring, and N-nitrosomethylurea 24.8
A 300d solution of diazomethane in ether prepared from f (0,241 mol) is added dropwise over about 40 minutes. after that,
Stir for about 30 minutes under water cooling.

Excess diazomethane is decomposed with acetic acid, the solvent is distilled off, and the obtained solid is recrystallized from methanol to obtain the target compound A.
32 (syn fJ) was obtained (27.Of, yield 70.4). 71.0-73.0°C.

The above-mentioned Kajimonoya 32 5.0ri) was dissolved in luene 2001M1, degassed by bubbling nitrogen gas, and then irradiated for 3 hours with a high-pressure mercury lamp (Rigaku Santo UVL-1009). The solvent was distilled off, and the entire residue was purified by column chromatography (silica gel-〇-hexane-ethyl acetate 2:1) to obtain the isomer (antiq) of the target compound A32.
1 was obtained (3.5 f, yield 70.0, mp 84.
5-85.5).

Example 2. [ethyl 0-methoxycarbonylmethyl
Production of 5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2-nitrobenzohydroxymate (compound 53)] 2.25 t of hydroxamate obtained in the same manner as in Synthesis Example 1 (5 mmol), anhydrous potassium carbonate 0.83 F (6 mmol), DMFl
Suspension solution of o-g k % b s ~ 67°C ML, p
-Toluenesulfonic acid ethyl ester 1.2 f (
6 mmol) was added dropwise in about 15 minutes. Then at the same temperature 1
Stir for an hour. The reaction mixture was poured into ice water with a weight of about 150 mm, extracted twice with 30 mm of ethyl acetate, washed with saturated brine, and dried over magnesium sulfate. After all the desiccant was filtered off, the solvent was distilled off and the resulting oily substance was subjected to column chromatography (
Purification with silica gel-n-hexane-ethyl acetate 4:l) yielded the desired compound 53 (syn type) (1
．． 4 f, yield 58.5%).

11D -1,5359° Table 1 shows the pyridyl phenyl ether M conductor represented by the general formula (1), which was constructed using a method similar to the above-mentioned example.

Table 1 XR”R”R physical property value 2, f(C)I! HC, Hs 3, HCHlH”-c3Ht 4, HCH8) I l-C3f-1゜5-
HCHI Hn C4H9m9.55-0~56-0
℃(anti) 6, HCH, H1-CJs't, )l CHx H5-c4u.

8, HCH8Ht-C4H.

9. HCHs Hncsf (Illo, H
CHl H1-CsHull, HCHs
CH, CH.

12, HCHa CHs C, He13,
HCHs CHs” C5Ht14, H
CM, CH, nee c, n.

15, HCHs CHx fl-Ca He
16, f(CHs CHat-CaHe1
7, HCkb CHI n CsH.

ls, HCH, C, H, CH3 19,) I CH, C, H, C2H.

20, HCHs C2H5n C2H527,
HCH3C2H6n-C, Hg22, HCtHs):I CHs23,
HC2H5He2) is 24, HC2H, Hn-c, H.

25, Ht-c, H, HCHs 26, kl I C”t(7HC2H527,
H 凰-C3H7Hlowe4H.

28, f(CzH,CFL C)is29,
HC, H, cH, n-C4)I.

30, Hi-C, H, CH, CH.

31, Hi-C, H7CH, n-C4H.

(anti) 38, CI CHs Hs-C, f(.

39, Cit CH, Ht-C<L41, α
CH,)it −C,)11゜42, CI
CH, CH3CHln"p'1.5328 (syn
)43, CJ? CH3CH, C2H.

44, CI CHl CHs” C3H
745, CI OH, CHli-C3H.

46, CI CHs CHI n-Ca
He47, CI CHI CHl t-C
4Hg48, OA' CH3CH1n-CsHl
.

49, CA' CH, C, Hll CH.

50, CI CHI C2Ha CzHs
s i, CI CH, C, H, fl-c3) f.

52, CI CH3C2H5n-c4a.

53, CI C2Hi HcH, 4・1l-535
9(Syn)54, CI C2H6HCzHss
5, CI C2HII H1l-C4Hs56,
C1i-C, Ht f-I C)i, n
2A・11.5336(syn)57-CJ i
-c, a, Hc, a.

58, CJ t-c, a, Hn-C4H.

59, CI C2H, CHs CH160, C
I C2H@CHs nc, a.

61, C1i-C, H, CH, OH.

62, cit 1-C3H, 0M3ne-e, H.

63, F CH, HCH3 64, F CHs HC1H665, F C
Hs Hn C5Ht66, F CH,H
i-c, H.

67, F CHs Hn-C4H.

68, F CHB f(1-04He69
, F CH, Hs-C, H.

Among the above compounds, X is (:J, R'' is CH, R2 is H
and R is lower alkyl, especially R
is preferably CHj or CH2C)(,).

Another active ingredient of the herbicidal composition of the present invention is 1,1'-dimethyl-4,4'-bipyridium dichloride (paraquat), which can be produced by known methods.

The herbicide composition of the present invention can control various weeds growing in non-agricultural land and agricultural land. For example, wild grass, black-tailed grass, foxtail grass, black-and-white grasshopper, black-and-white grasshopper, black-and-white grasshopper, Japanese hissers, vertical grasses, pigweed, whitewort, commonweed, morning glories, white-spotted fir, pigweed, sperihyu, American helium, American hornwort, yellowtail grass, dogbrush, red-winged deer, oxalis. , Chickweed, Chickweed, Chickweed, Tumefusa, Shepherd's purse, Tanetsukepana, Yaemugura, Hobby, Chamomile, Ezono Fox Thistle, Marigold, Hotokenoza, Inunoaguri, Himejong, Himemukashi mugwort,
It can control terrestrial narrow-leaved and broad-leaved weeds such as Prunus chinensis. Furthermore, aquatic narrow-leaved and broad-leaved weeds such as Japanese wild grass, Japanese cypress, Japanese cypress, Japanese azalea, Japanese chickweed, Japanese chickweed, Japanese fireweed, and Japanese grasshopper can also be controlled.

The herbicide composition of the present invention can be used not only on non-agricultural land, but also in a treatment method designed to prevent the chemical from coming into contact with the leaves and foliage of useful plants ([)irect 5play].

The herbicidal composition of the invention comprises the active ingredient and a carrier comprising a known liquid diluent, emulsifying, dispersing, wetting the active fraction,
Preparations that use surfactants and other auxiliary agents for the purpose of spreading, binding, adjusting disintegration, making the active ingredient cheaper, improving fluidity, preventing N, etc., and are commonly used as pesticides. It is used in the form of, for example, an emulsion, an aqueous solution, or a cloapure. It can also be used in combination or in combination with other agricultural chemicals such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

Examples of the liquid diluent include paraffinic hydrocarbons such as crocin, mineral oil, spindle oil, and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and methylnaphthalene; and carbon tetrachloride. Chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene, O-chlorotoluene; Ethers such as dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, acetic acid amyl, ethylene glycol acetate, diethylene glycol acetate,
Esters such as diptyl maleate and diethyl succinate; alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, and benzyl alcohol; ethylene glycol ethyl ether, ethylene glycol phenyl ether,
Examples include ether alcohols such as diethylene glycol ethyl ether and diethylene glycol butyl ether, polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Examples of surfactants that may be used include nonionic, anionic, cationic, and zwitterionic surfactants, but typically nonionic and ) anionic ones are used. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; those obtained by adding ethylene oxide to alkyl phenols such as isooctylphenol and nonylphenol; Products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid; Monomers such as stearyl phosphoric acid and dilauryl phosphoric acid. Products obtained by polyaddition of ethylene oxide to dialkyl phosphoric acid; products obtained by polymerization and addition of ethylene oxide to amines such as dodecylamine and stearate; higher fatty acid esters of polyhydric alcohols such as sorbitan, and polymerization addition of ethylene oxide to them. Products: Examples include products obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; alkyl sulfone ams such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate; Examples include aryl sulfonates such as sodium globylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzenesulfonate.

Furthermore, in order to improve the properties of the formulation of the herbicidal composition of the present invention and increase the shedding effect, high-quality ingredients such as casein, gelatin, albumin, glue, sodium alginate, carboxymethylcellulose (CMC), methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, etc. Molecular adjuncts and other adjuvants can also be used in combination.

The carrier and various adjuvants listed above. Considering the dosage form of the Fi preparation, the application situation, etc., depending on the purpose, Vi
It can be used as needed.

The active ingredient content of the herbicidal composition of the present invention in each of the thus obtained formulations varies depending on the formulation, but for example, the content of the compound represented by the general formula (I) and The weight of paraquat is 0.1 to 99 in winter, preferably 1 to 80 in winter.

Emulsions, for example, usually contain 1 to 301 L of active ingredients.
The coll contains about 5 to 20% by weight of an emulsifier, and the remainder is a liquid carrier, and a rust preventive agent is added as necessary.

Irrigation agents, for example, usually contain 25 to 80 parts of additives as active ingredients, and the remainder is a solid carrier, a dispersion wetting agent, and if necessary, a protective colloid agent, a thixotrope agent, an antifoaming agent, etc. are added. It will be done.

Flowable agents usually contain 1 to 3 active ingredients, for example.
Contains approximately 5 to 20 weight surfactants, and the remaining n% requires water, organic solvents, antifoaming agents, thickeners, antifreeze agents, bird deterrents, etc. added by

The herbicidal composition of the present invention contains 1 ml or more of the compound represented by the above general formula (1), paraquat, and KW effective acid components, and the usage ratio is 9 parts by weight of paraquat.
When 0.05 part by weight or more, preferably 0.1 part by weight or more is used, the effective amount of paraquat for feces can be effectively reduced. Furthermore, it is preferable to use 0.05 to 7 parts by weight, preferably 0.1 to 5 parts by weight, particularly 0.2 to 1 part by weight per 1 part by weight of paraquat. The effective fecal dosage of the compound that is derived from the general formula (1) is 10? /ha or more,
Up to about 1000f/ha, preferably 40 to 400
It is f7ha.

The herbicide composition of the present invention is prepared within the above usage ratio range,
It is preferable to apply a compound in which the synergistic herbicidal effect of the compound represented by the general formula (I) used in the present invention and paraquat is particularly large, and the effective fecal dosage of paraquat is also greatly reduced. It is. Of course, the selection can be changed as appropriate depending on the type of target weed, growth stage, application location, application time, nature, etc.

Next, several embodiments of formulation examples of the herbicidal composition of the present invention will be shown.

"Parts" in the following formulation examples are based on weight I/A-.

Formulation Example 1 A homogeneous mixed solution of 5 parts of Emulsion 432, 3 parts of polyoxyethylene styryl ether, 2 parts of alkylbenzene sulfonic acid, and 10 parts of xylene was added to 70 parts of an aqueous solution of Baraquat 24% by weight. After stirring gently for about 20 minutes using a homogenizer (rotation speed: 25,000 rpm) to obtain a uniform emulsion, propylene glycol 10fR5't710 was added thereto and thoroughly shaken to obtain an emulsion.

Expanding Agent Example 2 Wettable powder: 83.3 parts of a 24% aqueous solution of paraquat and 3 parts of alkylphenyl ether, 26 parts of white carbon, and 39 parts of clay.
After adding it dropwise into the mixture and mixing well,
Dry with warm air at ℃. Further, 1 part of Compound Mu 33 and 2 parts of polyoxyethylene alkylamine were added and mixed with thorough stirring.
Subsequently, it was finely pulverized using a jet mill (Albine Sharif) to obtain an irrigation agent.

Formulation Example 3, 5 parts of Flowable Compound 35, 20 parts of paraquat, 2 parts of polyoxyethylene nonylphenyl ether, 3 parts of dialkyl sulfosinenate, 20 parts of 1% CMC, 10 parts of propylene glycol and 40 parts of water. The mixture was mixed and ground in a wet ball mill to obtain a flowable agent.

Test Example 1 Part 1: Weeding effect test by foliage treatment: King grass (X height approx. 40 cm), foxtail grass (plant height approx. 40 cm),
A field where giant knotweed (plant height approximately 50crR) was uniformly grown was divided into 1++s and 2m test plots.

For the chemical treatment, the water conservancy prepared according to Spreading Agent Example 2 was added to water containing 25'l of ``Surfactant WKJ (Kao Corporation M)'' rO as a spreading agent so that the amount of active ingredients was as shown in Table 1. It was diluted and sprayed uniformly on the leaves and foliage at an amount of water equivalent to 100,017 ha.

One week, two weeks, four weeks, and eight weeks after the chemical spraying, the herbicidal effect on each weed was judged according to the following criteria, and the results are shown in Table 2.

Evaluation criteria (11 steps)

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) However, in the formula, R and R^1 each represent a lower alkyl group, and R^2 is a hydrogen atom or a lower alkyl group. 2-nitro-5-(substituted pyridyloxy) represented by a group, and X represents a hydrogen atom or a halogen atom
A herbicidal composition comprising as active ingredients one or more compounds selected from benzohydroxymic acid derivatives and 1,1'-dimethyl-4,4'-bipyridinium dichloride.